CN103261166A - Method for producing 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing compositions - Google Patents
Method for producing 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing compositions Download PDFInfo
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- CN103261166A CN103261166A CN2011800609512A CN201180060951A CN103261166A CN 103261166 A CN103261166 A CN 103261166A CN 2011800609512 A CN2011800609512 A CN 2011800609512A CN 201180060951 A CN201180060951 A CN 201180060951A CN 103261166 A CN103261166 A CN 103261166A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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Abstract
A method for producing 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing compositions, wherein the content of primary amine with respect to the total weight of the composition is 1 mass% or less, the method comprising a process of bringing a mixture containing 2,2,4-trimethyl-1,2-dihydroquinoline and a polymer thereof and, with respect to 100 parts by mass of the total of same, 2-6 parts by mass of a primary amine, into contact with 3-10 moles of a carboxylic acid anhydride with respect to 1 mole of the primary amine.
Description
Technical field
The present invention relates to contain the manufacture method of the composition of 2,2,4 trimethyl 1,2 dihydroquinoline polymer.
Background technology
In the Japanese kokai publication sho 53-145854 communique, the antiaging agent that used vulcanized rubber is used in the manufacturing as automobile tyre discloses the condensation reaction products of aniline and acetone.
Disclose primary amine content in the Japanese kokai publication hei 6-228375 communique and for the total amount of composition be and contained 2 below the 1 quality %, 2,4-trimethylammonium-1, the composition of 2-dihydroquinoline polymkeric substance, and then, as its manufacture method, the method that comprises following operation is disclosed also: from comprising 2,2,4-trimethylammonium-1 passes through distillation with 2,2 in 2-dihydroquinoline and the mixture of polymers thereof, 4-trimethylammonium-1, the operation that the 2-dihydroquinoline is taken out and make before take out in the operation 2,2,4-trimethylammonium-1, the 2-dihydroquinoline is carried out the operation of polymerization.
Summary of the invention
The invention provides following scheme:
[1] a kind of primary amine content is to contain 2 below the 1 quality % for the total amount of composition, 2,4-trimethylammonium-1, the manufacture method of the composition of 2-dihydroquinoline polymkeric substance, it comprises: make to comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and the operation that contacts with the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine with respect to the mixture that for their total 100 mass parts is the primary amine of 2～6 mass parts.
[2] according to [1] described manufacture method, it comprises:
Make acetone and aniline reaction, obtain comprising 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and be the operation of mixture of the primary amine of 2～6 mass parts for their total 100 mass parts; And
The operation that the mixture that makes gained contacts with the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine.
[3] a kind ofly contain 2,2,4-trimethylammonium-1, the composition of 2-dihydroquinoline polymkeric substance, it is characterized in that, be to contain 2,2,4-trimethylammonium-1 by what [1] or [2] described manufacture method obtained, the composition of 2-dihydroquinoline polymkeric substance, wherein, when obtaining forming composition by following preparation method, be below 0.5% 100 ℃ of following optical transmission rates with this forming composition insulation 600nm after 1 hour;
The preparation method of described forming composition is:
Contain composition 2 mass parts and insoluble sulphur 2 mass parts of 2,2,4 trimethyl 1,2 dihydroquinoline polymer by in divinyl rubber 100 mass parts, cooperating, thereby obtain title complex, prepare the thick forming composition of 2mm by this title complex.
[4] a kind of rubber combination, it is by for crude rubber 100 mass parts in being selected from natural rubber and diene series rubber, cooperate insoluble sulphur 2～10 mass parts and contain 2 by what [1] or [2] described manufacture method obtained, 2,4-trimethylammonium-1, composition 0.5～5 mass parts of 2-dihydroquinoline polymkeric substance and obtaining.
[5 compositions that contain 2,2,4 trimethyl 1,2 dihydroquinoline polymer that obtain by [1] or [2] described manufacture method are as the ageing-resistant purposes of tire.
[6] condensation reaction products of aniline and acetone and carboxylic acid anhydride are mixed and the composition that obtains is used for improving the stable on heating purposes that vulcanized rubber has.
[7] comprise following operation (1), (2) and stable on heating improvement method (3), that vulcanized rubber has;
(1) make and comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and the operation that contacts with the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine with respect to the mixture that for their total 100 mass parts is the primary amine of 2～6 mass parts,
(2) mixture, rubber constituent and the sulphur composition that obtains in the operation (1) carried out mixing operation,
(3) make the mixing thing sulfuration that obtains in the operation (2) and the operation that obtains vulcanized rubber.
[8] according to [7] described improvement method, wherein,
Operation (1) is implemented under the condition that does not have rubber constituent.
[9] according to [7] or [8] described improvement method, wherein,
Operation (1) is implemented under the condition that does not have the sulphur composition.
[10] according to each described improvement method in [7]～[9], wherein,
The usage quantity of the carboxylic acid anhydride in the operation (1) is 0.6～5 mole for the condensation reaction products 1kg of aniline and acetone.
[11] a kind of vulcanized rubber improved heat resistance agent, it obtains by the condensation reaction products of aniline and acetone and carboxylic acid anhydride are mixed.
[12] according to the improved heat resistance agent of [11] described vulcanized rubber, wherein,
The condensation reaction products of aniline and acetone is for comprising 2,2,4-trimethylammonium-1,2-dihydroquinoline, 2,2,4-trimethylammonium-1, the polymkeric substance of 2-dihydroquinoline, and the mixture of primary amine.
[13] according to [11] or [12] described vulcanized rubber improved heat resistance agent, wherein,
The condensation reaction products of aniline and acetone is for comprising 2,2,4-trimethylammonium-1,2-dihydroquinoline, 2,2,4-trimethylammonium-1, the polymkeric substance of 2-dihydroquinoline and with respect to 2,2,4-trimethylammonium-1,2-dihydroquinoline and 2,2,4-trimethylammonium-1, total 100 mass parts of the polymkeric substance of 2-dihydroquinoline are the mixture of the primary amine of 2～6 mass parts.
[14] according to [12] or [13] described vulcanized rubber improved heat resistance agent, it is by being that 3～10 moles carboxylic acid anhydride mixes and gets with the condensation reaction products of aniline and acetone with for 1 mole of the contained primary amine of aniline and the condensation reaction products of acetone.
[15] according to each described vulcanized rubber improved heat resistance agent in [11]～[14], wherein,
The condensation reaction products of aniline and acetone is for by making aniline and acetone carry out the product that condensation reaction produces under the condition that does not have the sulphur composition.
Embodiment
At first, be the manufacture method of the composition that contains 2,2,4 trimethyl 1,2 dihydroquinoline polymer below the 1 quality % for the total amount of composition for primary amine content, describe.Described manufacture method comprises: make to comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and for their total 100 mass parts be the primary amine of 2～6 mass parts mixture (below, be recited as sometimes " refining mixture ".) operation that contacts with the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine.
＜not refining mixture 〉
2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof mainly have the structure shown in the following formula (I).
(in the formula, n represents the integer more than 0.N is preferably 0～5 integer.)
2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof preferably by acetone and aniline reaction are made, are more preferably made by the dehydration polycondensation that aniline and acetone are reacted under heated condition in the presence of an acidic catalyst.In described reaction, preferably for 1 mole of aniline, use 2～20 moles in acetone.After with aniline and an acidic catalyst mixing, then excessive acetone is supplied in the mixture of gained continuously, unreacted acetone reclaims by distillation with the water of generation, and this keeps the viewpoint of temperature of reaction under normal pressure be preferred.
The reaction of acetone and aniline is implemented in the presence of an acidic catalyst usually.As an acidic catalyst, can list hydrogen halide such as hydrogenchloride, hydrogen bromide, hydrogen fluoride, organic acids such as organic sulfonic acid reach Lewis acids such as boron fluoride.Be preferably hydrogen halide, hydrogenchloride more preferably.An acidic catalyst can use with the form of the aqueous solution, also can use with the form of the liquid beyond the aqueous solution, can also use with the form of solid, also can import in the reaction system with the form of gas.Under the situation of using hydrogen halide, preferably use its aqueous solution.Under the situation of using hydrochloric acid, preferably its concentration is 15～35 quality %.The usage quantity of an acidic catalyst is 0.05～0.5 mole for 1 mole of aniline preferably.If the usage quantity of an acidic catalyst is more than 0.05 mole, then the reaction times can shorten, if below 0.5 mole, then n is that the quantitative change of the polymkeric substance 2 or more is few in the above-mentioned formula (I), so the ageing resistance raising.
The reaction of acetone and aniline can not have in the reaction for acetone and aniline active organic solvent in the presence of implement, but preferably do not implemented in fact with an organic solvent.Temperature of reaction is preferably 100～150 ℃ scope.If temperature of reaction is more than 100 ℃, then the quantitative change of unreacted aniline is few, 2,2,4-trimethylammonium-1, and the amount of 2-dihydroquinoline and polymkeric substance thereof increases.If temperature of reaction is below 150 ℃, then the usage quantity of acetone can reduce, and is preferred economically.
Described reaction is finished in 2～16 hours reaction times usually.If use relatively large an acidic catalyst, then the reaction times becomes shorter.
Reaction end is analyzed the aniline content in the reaction mixture by the common analysis means of high performance liquid chromatography, gas-chromatography etc., thereby suitably determines to get final product.
Behind the reaction terminating, preferably remove catalyzer in the reaction mixture by methods such as neutralizations, then remove organic solvent and unreacted aniline by under reduced pressure distilling, thereby take out refining mixture.
Usually comprise 2 in the reaction mixture of gained, 2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and for their total 100 mass parts, be the primary amine of 2～6 mass parts, it directly can be used for manufacture method of the present invention as not refining mixture, can also remove above-mentioned an acidic catalyst by aftertreatments such as neutralizing, wash, concentrate, thereby the mixture of gained is used for manufacture method of the present invention as refining mixture.
In this specification sheets, " primary amine " refers to mainly be caused by aniline and the primary amine that generates that described primary amine can adopt various structures, but as typical example, can list following formula (II) and (III) shown in two compounds of structure.
(in the formula, m represents the integer more than 0.)
Thus, " primary amine " in this specification sheets is the general name of multiple compound, and the content of primary amine is by whole primary amine being considered as aniline (molecular weight: the amount of 93.13) expressing.That is, with amino (NH
2) 1 mole be scaled primary amine 93.13g.The content of described primary amine is obtained as follows: specifically, make mixture be dissolved in chloroform, further add hydrochloric acid and Paradimethylaminobenzaldehyde, prepare sample solution, measure the absorbancy of the sample solution of gained, obtain by the calibration curve that has used aniline.
＜primary amine content is the composition that contains 2,2,4 trimethyl 1,2 dihydroquinoline polymer (following be recited as sometimes " the refining back composition " below the 1 quality % for the total amount of composition.) and manufacture method
Be that 3～10 moles carboxylic acid anhydride contacts by making refining mixture and 1 mole of speech of primary amine contained with respect to this mixture, thereby obtain making with extra care composition afterwards.
As carboxylic acid anhydride, can list the intramolecular acid anhydride of aromatic dicarboxylic acids such as Tetra hydro Phthalic anhydride, pyromellitic dianhydride, the intramolecular acid anhydride of aliphatic dicarboxylic acids such as succinyl oxide, Pyroglutaric acid, maleic anhydride, the intermolecular acid anhydrides of aliphatic carboxylic acids such as acetic anhydride, and the intermolecular acid anhydrides of aromatic carboxylic acid such as st-yrax acid anhydrides.In the middle of these, the intramolecular acid anhydride of optimization aromatic dicarboxylic acid or the intramolecular acid anhydride of aliphatic dicarboxylic acid, the more preferably intramolecular acid anhydride of aromatic dicarboxylic acid, especially preferably Tetra hydro Phthalic anhydride.
The usage quantity of carboxylic acid anhydride is 3～10 moles for 1 mole of the contained primary amine of refining mixture, is preferably 3～5 moles.
Refining mixture can be implemented in the presence of the solvent that does not have activity for the reaction made from extra care mixture and carboxylic acid anhydride with contacting of carboxylic acid anhydride, also can not use described solvent ground to be implemented in fact.As described solvent, can list aromatic hydrocarbon solvents such as dimethylbenzene, toluene, reach aliphatic hydrocarbon solvents such as heptane, octane, dimethylhexane.Under the situation of using solvent, its usage quantity is generally 0.5～10 mass parts for not refining mixture 1 mass parts, be preferably 0.5～2 mass parts.
Not refining mixture is implemented under the condition that does not have the sulphur composition with contacting preferably of carboxylic acid anhydride.
Not refining mixture is implemented under the condition that does not have rubber constituent with contacting preferably of carboxylic acid anhydride.
Not refining mixture is preferably 100～150 ℃ with the temperature that contacts of carboxylic acid anhydride.Reaction end can be determined reaction mixture analysis by for example utilizing high performance liquid chromatography etc.
By as required the mixture of gained being implemented neutralization, washing, processing such as concentrated, can take out refining back composition.
＜rubber combination 〉
Rubber combination of the present invention is by for crude rubber 100 mass parts in being selected from natural rubber and diene series rubber, cooperates insoluble sulphur 2～10 mass parts and refining back composition 0.5～5 mass parts and obtains.
As natural rubber, can list unmodified natural rubber, epoxy natural rubber, DPNR, reach other modified natural rubbers.
As diene series rubber, can list phenylethylene/butadiene copolymer rubber, the contour nonsaturation rubber of polybutadiene rubber.
Insoluble sulphur refers to the sulphur to the insoluble unbodied polymer shape of dithiocarbonic anhydride, and its usage quantity is generally 2～10 mass parts, is preferably 3～6 mass parts for crude rubber 100 mass parts.
The usage quantity of refining back composition is generally 0.5～5 mass parts, is preferably 0.5～2 mass parts for crude rubber 100 mass parts.
Rubber combination of the present invention can also comprise weighting agent, vulcanization accelerator, zinc oxide, fatty acid, cobalt salt etc.
As weighting agent, can list normally used carbon black, silicon-dioxide, talcum, clay, aluminium hydroxide, titanium oxide etc. in the rubber materials, preferably use carbon black and silicon-dioxide, more preferably use carbon black.The usage quantity of described weighting agent is unqualified, but is preferably the scope of 5～100 mass parts for crude rubber 100 mass parts, is preferably the scope of 30～80 mass parts especially.
As carbon black, can list Japan rubber association and compile the carbon black of " rubber industry brief guide (go system industry Bian list)＜the 4th edition〉" the 494th page of record, be preferably HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), FEF (Fast Extrusion Furnace), MAF, GPF (General Purpose Furnace), SRF carbon blacks such as (Semi-Reinforcing Furnace).
As silicon-dioxide, can list CTAB specific surface area 50～180m
2The silicon-dioxide of/g, nitrogen adsorption specific surface area 50～300m
2The silicon-dioxide of/g is preferably Tosoh Silica Corporation system " AQ ", " AQ-N ", Degussa corporate system " Ultrasil (registered trademark) VN3 ", " Ultrasil (registered trademark) 360 ", " Ultrasil (registered trademark) 7000 ", Rhodia corporate system " ZEOSIL (registered trademark) 115GR ", " ZEOSIL (registered trademark) 1115MP ", " ZEOSIL (registered trademark) 1205MP ", " ZEOSIL (registered trademark) Z85MP ", Japanese Silica corporate system commercially available products such as " Nipsil (registered trademark) AQ ".In addition, also the preferred pH that cooperates is that 6～8 silicon-dioxide, the silicon-dioxide that comprises sodium 0.2～1.5 quality %, circularity are 1～1.3 spherical silicon dioxide, dimethyl-silicon wet goods silicone oil, contain the silicoorganic compound of (ethoxymethyl) silylation, the silicon-dioxide that utilizes alcohol such as ethanol or polyoxyethylene glycol to carry out the silicon-dioxide after the surface treatment, had the different nitrogen adsorption specific surface area more than two kinds.
Under the situation that cooperates silicon-dioxide, preferably for crude rubber 100 mass parts, cooperate carbon black 5～50 mass parts, the cooperation ratio of silicon-dioxide/carbon black is preferably 0.7/1～1/0.1 especially.Using under the situation of silicon-dioxide as weighting agent, preferred add two (3-triethoxysilylpropyltetrasulfide) tetrasulfides (Degussa corporate system " Si-69 "), two (3-triethoxysilylpropyltetrasulfide) disulphide (Degussa corporate system " Si-75 ") etc. have can with the compound of functional groups such as element such as the silicon of silica bound or organoalkoxysilane, so-called silane coupling agent.
As aluminium hydroxide, can list nitrogen adsorption specific surface area 5～250m
2The aluminium hydroxide of/g, DOP give the aluminium hydroxide of oil mass 50～100mL/100g.
As vulcanization accelerator, can list rubber industry brief guide (industry of go system is list just)＜the 4th edition〉thiazole of record is that vulcanization accelerator, sulfinyl amine are that vulcanization accelerator and guanidine are vulcanization accelerator in (Japan rubber association of Corporation distribution on January 20th, 1994) the 412nd～413 page.
Specifically, can list N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine (CBS), the N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine (BBS), N, N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine (DCBS), 2-mercaptobenzothiazole (MBT), bisbenzothiazole based bisulfide (MBTS) and vulkacit D (DPG).In addition, can also use morpholine disulphide as known vulcanizing agent.Using under the situation of carbon black as weighting agent, preferably with N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine (CBS), the N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine (BBS), N, any in N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine (DCBS) and the bisbenzothiazole based bisulfide (MBTS) and vulkacit D (DPG) are also used.As weighting agent and under the situation with silicon-dioxide and carbon black and usefulness, preferably with N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine (CBS), the N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine (BBS), N, any in N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine (DCBS) and the bisbenzothiazole based bisulfide (MBTS) and vulkacit D (DPG) are also used.
The usage quantity of described vulcanization accelerator is unqualified, is preferably 0.5～5 mass parts for crude rubber 100 mass parts, is preferably 0.5～2 mass parts especially.
The usage quantity of zinc oxide is preferably 1～15 mass parts, 3～8 mass parts more preferably for crude rubber 100 mass parts.
As fatty acid, preferred stearic acid, its usage quantity is preferably 1～15 mass parts, 1～7 mass parts more preferably for crude rubber 100 mass parts.
As cobalt salt, can list cobalt naphthenate.For its usage quantity, as the cobalt composition, for crude rubber 100 mass parts, be preferably 0.02～2 mass parts, 0.1～0.5 mass parts more preferably.
Further as required can be with normally used various rubber reagent in the rubber industry, for example anti-degradation, linking agent, retarder (retarder), peptizer, tenderizer, petroleum resin, lubricant, plasticizer, tackifiers, Resorcinol or Resorcinol are the such caking agent of resin etc. and use.
Usually, the cooperation of rubber is undertaken by two operations.Namely, cooperate crude rubber, weighting agent, refining back composition and as required and the 1st operation of the zinc oxide that adds etc. under than higher high temperature, and under lower low temperature, cooperate insoluble sulphur and as required and the 2nd operation of the vulcanization accelerator that adds etc.
The cooperation temperature of the 1st operation is preferably 80～200 ℃, more preferably 110～160 ℃.
The cooperation temperature of the 2nd operation is preferably 60～110 ℃.
The rubber combination of the present invention that cooperates thus is particularly suitable for the internal part of automobile tyre.As the internal part of automobile tyre, can list belt (belt), carcass, air retaining wall and undertread.
In the rubber combination of the present invention, refining back composition can be used as the tire antiaging agent.
Rubber combination of the present invention vulcanizes after processed under the specific state, becomes target product thus.
The condition of sulfuration is different because of the difference of target product, selects in the scope about 120～200 ℃, the scope about 1 minute～2 hours usually.
With regard to the composition of refining back, be below the 1 quality % by the primary amine content for total composition, thereby not dissolving of insoluble sulphur in above-mentioned the 2nd operation, but in rubber combination, disperse equably, begin dissolving in the stage of sulfuration, therefore, sulphur is difficult for being present on ground partially rubber combination surface (following be recited as sometimes " bloom (bloom) ".), its result exists in rubber combination inside and obtains the such advantage of sufficient cure efficiency easily.
The solvability evaluation of＜insoluble sulphur 〉
For the solvability of insoluble sulphur, big by the caused influence of refining back composition, can estimate as described below.That is, when obtaining forming composition by following preparation method, as if being below 0.5% 100 ℃ of following optical transmission rates with this forming composition insulation 600nm after 1 hour, then insoluble sulphur dissolves hardly, is preferably so refining back composition.
The preparation method of＜forming composition 〉
Make with extra care back composition 2 mass parts and insoluble sulphur 2 mass parts by in divinyl rubber 100 mass parts, cooperating, thereby obtain title complex, prepare the thick forming composition of 2mm by this title complex.
Then, for the condensation reaction products of aniline and acetone and carboxylic acid anhydride are mixed composition be used for improving the stable on heating improvement method that stable on heating purposes that vulcanized rubber has and vulcanized rubber have, describe.
The stable on heating improvement method that vulcanized rubber of the present invention has comprises following operation (1), (2) and (3).
(1) makes and comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and the operation that contacts with the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine with respect to the mixture that for their total 100 mass parts is the primary amine of 2～6 mass parts.
(2) mixture, rubber constituent and the sulphur composition that obtains in the operation (1) carried out mixing operation.
(3) make the mixing thing sulfuration that obtains in the operation (2) and the operation that obtains vulcanized rubber.
In this specification sheets, " improving the thermotolerance that vulcanized rubber has " refers to, in the oven test (JIS K6257) of vulcanized rubber, changes the tensile properties (JIS K6251) of test film.
Below, for above-mentioned each operation (1), (2) and (3), describe respectively.In addition, by this explanation, the composition that obtains for the condensation reaction products of aniline and acetone and carboxylic acid anhydride are mixed also describes for improving the described invention of stable on heating purposes that vulcanized rubber has.
At first, for above-mentioned operation (1), namely, make and comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and with respect to the mixture and the operation that the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine contacts that for their total 100 mass parts are the primary amine of 2～6 mass parts describe.
Comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and be the condensation reaction products that the mixture of the primary amine of 2～6 mass parts is preferably aniline and acetone for their total 100 mass parts.
Aniline comprises the condensation reaction products (being generally the mixture of the compound that n is different in the above-mentioned formula (I)) of the aniline shown in the above-mentioned formula (I) and acetone as main component with the condensation reaction products of acetone.
The condensation reaction products of aniline and acetone is preferably by with respect to 2～20 moles in 1 mole of aniline speech use acetone, and make their the reaction and obtain, more preferably in the presence of an acidic catalyst, make by the dehydration polycondensation that aniline and acetone are reacted under heated condition.After mixing aniline and an acidic catalyst, then excessive acetone is supplied in the mixture of gained continuously, unreacted acetone reclaims by distillation with the water that generates, and this keeps the viewpoint of temperature of reaction under normal pressure be preferred.
The reaction of acetone and aniline is implemented in the presence of an acidic catalyst usually.As an acidic catalyst, can list hydrogen halide such as hydrogenchloride, hydrogen bromide, hydrogen fluoride, organic acids such as organic sulfonic acid reach Lewis acids such as boron fluoride.Be preferably hydrogen halide, hydrogenchloride more preferably.An acidic catalyst can use with the form of the aqueous solution, also can use with the form of the liquid beyond the aqueous solution, can also use with the form of solid, also can import to the form of gas in the reaction system.Under the situation of using hydrogen halide, preferably use its aqueous solution.Under the situation of using hydrochloric acid, its concentration is preferably 15～35 quality %.The usage quantity of an acidic catalyst is preferably 0.05～0.5 mole for 1 mole of aniline.If the usage quantity of an acidic catalyst is more than 0.05 mole, then the reaction times can shorten, if below 0.5 mole, then the n in the above-mentioned formula (I) is that the quantitative change of the polymkeric substance 2 or more is few, so the ageing resistance raising.
The reaction of acetone and aniline can not have in the reaction for acetone and aniline active organic solvent in the presence of implement, can also substantially do not implemented with an organic solvent.Temperature of reaction is preferably 100～150 ℃ scope.If temperature of reaction is more than 100 ℃, then the quantitative change of unreacted aniline is few, 2,2,4-trimethylammonium-1, and the amount of 2-dihydroquinoline and polymkeric substance thereof increases.If temperature of reaction is below 150 ℃, then the usage quantity of acetone can reduce, and is preferred economically.
Described reaction is finished in 2～16 hours reaction times usually.If use than relatively large an acidic catalyst, then the reaction times becomes shorter.
Reaction end is analyzed the aniline content in the reaction mixture by common analysis means such as high performance liquid chromatography, gas-chromatography and is suitably determined to get final product.
Behind the reaction terminating, preferably remove catalyzer in the reaction mixture by methods such as neutralizations, then, organic solvent and unreacted aniline are removed in distillation under reduced pressure, thereby take out the condensation reaction products of aniline and acetone from reaction mixture.
The reaction mixture of gained can directly mix with carboxylic acid anhydride with the form of the condensation reaction products of acetone with aniline, also can be by neutralization, washing, aftertreatment such as concentrate and remove above-mentioned an acidic catalyst, the mixture of gained is mixed with carboxylic acid anhydride with the condensation reaction products of acetone as aniline.These condensation reaction products comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and be the primary amine of 2～6 mass parts for their total 100 mass parts.
As carboxylic acid anhydride, can list the intramolecular acid anhydride of aromatic dicarboxylic acids such as Tetra hydro Phthalic anhydride, pyromellitic dianhydride, the intramolecular acid anhydride of aliphatic dicarboxylic acids such as succinyl oxide, Pyroglutaric acid, maleic anhydride, the intermolecular acid anhydrides of aliphatic carboxylic acids such as acetic anhydride, and the intermolecular acid anhydrides of aromatic carboxylic acid such as st-yrax acid anhydrides.In the middle of these, the intramolecular acid anhydride of optimization aromatic dicarboxylic acid or the intramolecular acid anhydride of aliphatic dicarboxylic acid, the more preferably intramolecular acid anhydride of aromatic dicarboxylic acid, further preferred Tetra hydro Phthalic anhydride.
The usage quantity of carboxylic acid anhydride is preferably 3～10 moles, more preferably 3～5 moles for 1 mole of primary amine.
The usage quantity of carboxylic acid anhydride is preferably 0.6～5 mole, more preferably 0.6～2 mole for the condensation reaction products 1kg of aniline and acetone.If the usage quantity of carboxylic acid anhydride is in above-mentioned scope, then by carrying out mixing to the condensation reaction products of aniline and acetone and carboxylic acid anhydride are mixed the composition, rubber constituent and the sulphur composition that get, then vulcanize, thereby it is the improved tendency of the thermotolerance that the vulcanized rubber that has gained has, so preferred.
Can not have in the reaction for this condensation reaction products and carboxylic acid anhydride the mixing of the condensation reaction products of aniline and acetone and carboxylic acid anhydride active solvent in the presence of implement, can substantially not use under the condition of described solvent yet and implement.As described solvent, can list aromatic hydrocarbon solvents such as dimethylbenzene, toluene, reach aliphatic hydrocarbon solvents such as heptane, octane, dimethylhexane.Under the situation of using solvent, its usage quantity is generally 0.5～10 mass parts, is preferably 0.5～2 mass parts for condensation reaction products 1 mass parts of aniline and acetone.
Aniline with under the condition that does not have the sulphur composition, implement condensation reaction products and the mixing preferably of carboxylic acid anhydride of acetone.For described sulphur composition, in operation (2), describe in detail.
Aniline with under the condition that does not have rubber constituent, implement condensation reaction products and the mixing preferably of carboxylic acid anhydride of acetone.
The condensation reaction products of aniline and acetone and the mixing temperature of carboxylic acid anhydride are preferably 100～150 ℃.
The composition of gained can be directly used in operation (2), be used further to operation (2) after the aftertreatment such as also can implement neutralization, washing as required, concentrate.Below the composition that will obtain so sometimes is recited as " this composition ".
Then, for operation (2), that is, composition (this composition), rubber constituent and the sulphur composition of gained in the operation (1) carried out mixing operation, describe.Below, sometimes the mixing thing that obtains in this operation is recited as " this rubber combination ".
As rubber constituent, can list the rubber that is selected from natural rubber and the diene series rubber.
As natural rubber, can list unmodified natural rubber, epoxy natural rubber, DPNR, reach other modified natural rubbers.
As diene series rubber, can list phenylethylene/butadiene copolymer rubber, the contour nonsaturation rubber of polybutadiene rubber.
As the sulphur composition, can list powder sulphur, precipitated sulfur, colloid sulphur, insoluble sulphur, reach polymolecularity sulphur.Be preferably powder sulphur, this rubber combination be used for be preferably insoluble sulphur under the situation of belt with the many tyre elements of sulfur contents such as parts.Its usage quantity is unqualified, for rubber constituent 100 mass parts, is preferably 2～10 mass parts, 3～6 mass parts more preferably.
The usage quantity of this composition is preferably 0.5～5 mass parts, 0.5～2 mass parts more preferably for rubber constituent 100 mass parts.
This rubber combination can also further comprise weighting agent, vulcanization accelerator, zinc oxide, fatty acid, cobalt salt etc.
As weighting agent, can list the identical weighting agent with aforementioned list, preferably use carbon black and silicon-dioxide, more preferably use carbon black.The usage quantity of described weighting agent is unqualified, for rubber constituent 100 mass parts, is preferably 5～100 mass parts, 30～80 mass parts more preferably.
As carbon black, can list with above-mentioned and enumerate identical carbon black, be preferably HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), FEF (Fast Extrusion Furnace), MAF, GPF (General Purpose Furnace), SRF carbon blacks such as (Semi-Reinforcing Furnace).
As silicon-dioxide, can list with above-mentioned and enumerate identical silicon-dioxide, be preferably Tosoh Silica Corporation system " AQ ", " AQ-N ", Degussa corporate system " Ultrasil (registered trademark) VN3 ", " Ultrasil (registered trademark) 360 ", " Ultrasil (registered trademark) 7000 ", Rhodia corporate system " ZEOSIL (registered trademark) 115GR ", " ZEOSIL (registered trademark) 1115MP ", " ZEOSIL (registered trademark) 1205MP ", " ZEOSIL (registered trademark) Z85MP ", Japan Silica corporate system commercially available products such as " Nipsil (registered trademark) AQ ".In addition, also the preferred pH that cooperates is that 6～8 silicon-dioxide, the silicon-dioxide that comprises sodium 0.2～1.5 quality %, circularity are the silicone oil of 1～1.3 spherical silicon dioxide, dimethyl-silicon wet goods, the silicon-dioxide that contains the silicoorganic compound of (ethoxymethyl) silylation, carried out the silicon-dioxide after the surface treatment, had the different nitrogen adsorption specific surface area more than two kinds with alcohol such as ethanol or polyoxyethylene glycol.
Under the situation that cooperates silicon-dioxide, for rubber constituent 100 mass parts, preferably cooperate carbon black 5～50 mass parts, the cooperation ratio of preferred especially silicon-dioxide/carbon black is 0.7/1～1/0.1.Using under the situation of silicon-dioxide as weighting agent, preferred add two (3-triethoxysilylpropyltetrasulfide) tetrasulfides (Degussa corporate system " Si-69 "), two (3-triethoxysilylpropyltetrasulfide) disulphide (Degussa corporate system " Si-75 ") etc. have can with the compound of functional groups such as element such as the silicon of silica bound or organoalkoxysilane, so-called silane coupling agent.
As aluminium hydroxide, can list with above-mentioned and enumerate identical aluminium hydroxide.
As vulcanization accelerator, can list with above-mentioned and enumerate identical vulcanization accelerator.Using under the situation of carbon black as weighting agent, preferably with N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine (CBS), the N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine (BBS), N, N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine (DCBS), any and vulkacit D (DPG) and use in the bisbenzothiazole based bisulfide (MBTS), as weighting agent and under the situation with silicon-dioxide and carbon black and usefulness, preferably with N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine (CBS), the N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine (BBS), N, N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine (DCBS), any and vulkacit D (DPG) and use in the bisbenzothiazole based bisulfide (MBTS).
The usage quantity of described vulcanization accelerator is unqualified, for rubber constituent 100 mass parts, is preferably 0.5～5 mass parts, 0.5～2 mass parts more preferably.
The usage quantity of zinc oxide is preferably 1～15 mass parts for rubber constituent 100 mass parts, more preferably 3～8 mass parts.
As fatty acid, be preferably stearic acid, its usage quantity is preferably 1～15 mass parts, 1～7 mass parts more preferably for rubber constituent 100 mass parts.
As cobalt salt, can list cobalt naphthenate.For its usage quantity, as the cobalt composition, for rubber constituent 100 mass parts, be preferably 0.02～2 mass parts, more preferably 0.1～0.5 mass parts.
Further, can also be as required and with normally used various rubber reagent in the rubber industry, for example anti-degradation, linking agent, retarder, peptizer, tenderizer, petroleum resin, lubricant, plasticizer, tackifiers, Resorcinol or Resorcinol are caking agent such as resin etc.
As each composition is carried out mixing step, can list to rubber constituent and weighting agent carry out mixing (below, be recited as sometimes " step 1 ".), then to the composition that obtains in the step 1 and sulphur composition carry out mixing (below, be recited as sometimes " step 2 ".) such step.This composition preferably carries out mixing in step 1.
The melting temperature of step 1 is preferably 80～200 ℃, more preferably 110～160 ℃.
The melting temperature of step 2 is preferably 60～110 ℃.
This rubber combination that obtains is particularly suitable for the internal part of automobile tyre thus.As the internal part of automobile tyre, can list belt, carcass, air retaining wall and undertread.
At last, for operation (3), that is, make the mixing thing (this rubber combination) that obtains by operation (2) vulcanize and obtain the operation of vulcanized rubber, describe.
This rubber combination is made as the product of target after processed under the specific state by sulfuration.
The condition of sulfuration is according to target product and difference, selects the common scope, the scope about 1 minute～2 hours from about 120～200 ℃.
Cooperate the condensation reaction products (not mixing with carboxylic acid anhydride) of aniline and acetone, obtain rubber combination, with its sulfuration and must vulcanized rubber compare, improve by the thermotolerance of this rubber combination being vulcanized the vulcanized rubber that gets.
Embodiment
Below, enumerate embodiment, test example, Production Example etc., specify the present invention, the present invention is not limited thereto.
In the following Production Example, for 2,2,4-trimethylammonium-1,2-dihydroquinoline (below be sometimes referred to as " TMDQ ") amount and TMDQ dipolymer amount, use Eclipse XDB-C18A as post respectively, as the water of A liquid, as the methyl alcohol of B liquid, analyzed by the high performance liquid chromatography based on gradient method.
Primary amine content is obtained as described below: make not refining mixture or refining back composition dissolves in chloroform, further add hydrochloric acid and Paradimethylaminobenzaldehyde, prepare sample solution, utilize spectrophotometer (measuring wavelength 440nm) to measure the absorbancy of this sample solution, obtain by the calibration curve that has used aniline.
Production Example 1
Add aniline 46.5g and 35 quality % hydrochloric acid 4.4g in the 300mL round-bottomed flask that thermometer, stirrer and water distilling apparatus are installed, the mixture of gained is warming up to 110 ℃.To wherein, following to 16 hours dropping acetone 290.4g at 110 ℃～140 ℃.The mixture of gained is incubated 4 hours down at 135 ℃～140 ℃.After the reaction mixture of gained is cooled to 90 ℃, use dilution with toluene, with in the aqueous sodium hydroxide solution and after, leave standstill separatory and remove water layer.After heating up in a steamer the toluene in the layer that deoils, by further under 200 ℃ of interior temperature, decompression degree 2mmHg, heating up in a steamer low boiling point component, thereby do not made with extra care mixture 80.3g.The not refining mixture of gained comprises the condensation reaction products of aniline and acetone in fact, contains TMDQ0.1 quality %, TMDQ dipolymer 14 quality % respectively.In addition, primary amine content is 3.2 quality %.
Embodiment 1
In the 100mL four-hole round-bottomed flask with thermometer, stirrer, Dean-Stark pipe and condenser, add not refining mixture 20.0g, the Tetra hydro Phthalic anhydride 4.83g and the dimethylbenzene 100mL that obtain in the Production Example 1.The mixture of gained is heated up in a steamer desolventizing in insulation under 140 ℃ after 5 hours, obtain refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, and primary amine content is 0.1 quality %.
Embodiment 2
Among the embodiment 1, replace Tetra hydro Phthalic anhydride 4.83g and use succinyl oxide 3.26g, making heat-retaining condition is 140 ℃ and 3 hours, in addition, implements similarly to Example 1, obtains refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reactant of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condenses of aniline and acetone, and primary amine content is 0.1 quality %.
Embodiment 3
Among the embodiment 1, replace the not refining mixture 20.0g that obtains in the Production Example 1 and use the not refining mixture (primary amine content: 10.0g 2.9 quality %) that obtains according to Production Example 1, replace Tetra hydro Phthalic anhydride 4.83g and use Tetra hydro Phthalic anhydride 1.75g, replace dimethylbenzene 100mL and use dimethylbenzene 20mL, making heat-retaining condition is 140 ℃ and 4 hours, in addition, implement similarly to Example 1, obtain refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, and primary amine content is 0.3 quality %.
Embodiment 4
Among the embodiment 3, replace dimethylbenzene 20mL and use toluene 20mL, making heat-retaining condition is 110 ℃, in addition, implements similarly to Example 3, obtains refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, and primary amine content is 0.2 quality %.
Embodiment 5
Among the embodiment 1, replace the not refining mixture 20.0g that obtains in the Production Example 1 and use the not refining mixture (primary amine content: 20.0g 3.5 quality %) that obtains according to Production Example 1, replace Tetra hydro Phthalic anhydride 4.83g and use Tetra hydro Phthalic anhydride 4.24g, replace dimethylbenzene 100mL and use dimethylbenzene 40g, making heat-retaining condition is 140 ℃ and 3 hours, in addition, implement similarly to Example 1, obtain refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, and primary amine content is 0.1 quality %.
Embodiment 6
Among the embodiment 5, replace dimethylbenzene 40g and use toluene 40g, making heat-retaining condition is 110 ℃, in addition, implements similarly to Example 5, obtains refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, and primary amine content is 0.1 quality %.
Embodiment 7
Add the refining mixture that obtains according to Production Example 1 (primary amine content: 2.9 quality %) 20.0g, and Tetra hydro Phthalic anhydride 3.46g in the 100mL four-hole round-bottomed flask with thermometer, stirrer, Dean-Stark pipe and condenser.Make the mixture of gained be incubated 2 hours down at 140 ℃, obtain refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, and primary amine content is 0.1 quality %.
Embodiment 8
Among the embodiment 7, making heat-retaining condition is 120 ℃ and 4 hours, in addition, implements similarly to Example 7, obtains refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, and primary amine content is 0.2 quality %.
Embodiment 9
Among the embodiment 7, the refining mixture that replacement obtains according to Production Example 1 (primary amine content: 20.0g and use the refining mixture (primary amine content: 20.0g 3.5 quality %) that obtains according to Production Example 1 2.9 quality %), replace Tetra hydro Phthalic anhydride 3.46g and use Tetra hydro Phthalic anhydride 4.24g, in addition, implement similarly to Example 7, obtain refining back composition.The refining back composition of gained in fact also comprises Tetra hydro Phthalic anhydride, reaches the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, and primary amine content is 0.0 quality %.
Reference example
Add the refining mixture that obtains according to Production Example 1 (primary amine content: 2.9 quality %) 25.0g, and Tetra hydro Phthalic anhydride 1.25g in the 100mL four-hole round-bottomed flask with thermometer, stirrer, Dean-Stark pipe and condenser.The mixture of gained is heated up in a steamer desolventizing in insulation under 140 ℃ after 3 hours, obtain composition.The composition of gained in fact also comprises Tetra hydro Phthalic anhydride, and the reaction product of primary amine and Tetra hydro Phthalic anhydride except comprising the composition from the condensation reaction products of aniline and acetone, primary amine content is 1.8 quality %.
[table 1]
Test example 1
By for divinyl rubber 100 mass parts, cooperate refining back composition 2 mass parts and insoluble sulphur 2 mass parts that obtain among the embodiment 1, thereby obtain title complex, this title complex is held on polyethylene terephthalate film processed and to be shaped to 2mm thick.The forming composition of gained is incubated 1 hour down at 100 ℃.The optical transmission rate of the 600nm of the forming composition after the insulation is 0.00%.
Test example 2～9
In the test example 1, replace the refining back composition that obtains among the embodiment 1 and use the refining back composition that obtains respectively among the embodiment 2～9, in addition, with test example 1 similarly, the forming composition after obtaining being incubated.With the insulation after forming composition 600nm the optical transmission rate with the test example 1 be shown in following table 2.
[table 2]
| The test example | Transmissivity (600nm)/% |
| 1 | 0.00 |
| 2 | 0.01 |
| 3 | 0.03 |
| 4 | 0.03 |
| 5 | 0.03 |
| 6 | 0.03 |
| 7 | 0.26 |
| 8 | 0.14 |
| 9 | 0.05 |
Reference test example 1
In the test example 1, replace the refining back composition that obtains among the embodiment 1 and use the refining mixture that obtains in the Production Example 1, in addition, with test example 1 similarly, the forming composition after obtaining being incubated.The optical transmission rate of its 600nm is 20.07%.
Reference test example 2
In the test example 1, replace the refining back composition that obtains among the embodiment 1 and use the composition that obtains in the reference example, in addition, with test example 1 similarly, the forming composition after obtaining being incubated.The optical transmission rate of its 600nm is 6.39%.
Embodiment 10: the manufacturing of rubber combination
＜the 1 operation 〉
Use Banbury (the smart machine-processed 600ml Labo Plasto Mill (ラ ボ プ ラ ス ト ミ Le) of Japan), cooperate refining back composition 2 mass parts that obtain among natural rubber (RSS#1) 100 mass parts, carbon black (N330) 45 mass parts, aqueous silicon dioxide (Nipsil AQ) 10 mass parts, stearic acid 3 mass parts, zinc oxide 5 mass parts and the embodiment 1 and carry out mixingly, obtain mixing thing.
＜the 2 operation 〉
Utilize mill, under 60～80 ℃ temperature, the mixing thing that cooperation obtains by the 1st operation, vulcanization accelerator (N, N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine) 0.7 mass parts, insoluble sulphur 6 mass parts (as the sulphur composition) and cobalt naphthenate 2 mass parts and carry out mixingly obtain rubber combination of the present invention.
＜the 3 operation 〉
By under 150 ℃, the rubber combination that obtains in the 2nd operation being carried out sulfidizing, obtain vulcanized rubber thus.
Embodiment 11 and 12
Among the embodiment 10, replace the refining back composition that obtains among the embodiment 1 and use the refining back composition that obtains among the embodiment 7,8 respectively, in addition, implement similarly to Example 10, obtain rubber combination of the present invention and vulcanized rubber.
Test example 10～12
For the rubber combination that obtains respectively among the embodiment 10～12 and vulcanized rubber, implement following test.The results are shown in following table 3.
1) rebound resilience: according to JIS K6255,25 ℃ of rebound resiliences of measuring vulcanized rubber down.
2) hardness: according to JIS K6253, use sclerometer A type, 25 ℃ of hardness of measuring vulcanized rubber down.
[table 3]
| The test example | Rebound resilience/% | Hardness/HS |
| 10 | 56 | 71 |
| 11 | 56 | 68 |
| 12 | 52 | 70 |
Production Example 2
In the 300mL round-bottomed flask that thermometer, stirrer and water distilling apparatus are installed, add aniline 46.5g and 35 quality % hydrochloric acid 4.4g, make the mixture of gained be warming up to 110 ℃.Descend with 16 hours to wherein dripping acetone 290.4g at 110 ℃～140 ℃.Make the mixture of gained be incubated 4 hours down at 135 ℃～140 ℃.The reaction mixture of gained is cooled to 90 ℃, uses dilution with toluene, with in the aqueous sodium hydroxide solution and after, leave standstill separatory and remove water layer.After heating up in a steamer the toluene in the layer that deoils, by under 200 ℃ of interior temperature, decompression degree 2mmHg, heating up in a steamer low boiling point component, thereby obtain the condensation reaction products 80.3g of aniline and acetone.
Production Example 3: operation (1)
Add in the 100mL four-hole round-bottomed flask with thermometer, stirrer, Dean-Stark device and condenser the aniline that obtains according to Production Example 2 and acetone condensation reaction products 25.0g, reach Tetra hydro Phthalic anhydride 3.46g.The mixture of gained is incubated 2 hours down at 140 ℃, obtains this composition.
Production Example 4: operation (1)
In the Production Example 3, making heat-retaining condition is 120 ℃ and 4 hours, in addition, similarly implements with Production Example 3, obtains this composition.
Production Example 5: operation (1)
In the 100mL four-hole round-bottomed flask with thermometer, stirrer, Dean-Stark device and condenser, the aniline that obtains in the adding Production Example 2 and condensation reaction products 20.0g, Tetra hydro Phthalic anhydride 11.2g and the dimethylbenzene 40.0mL of acetone.The mixture of gained is incubated 3 hours down at 140 ℃, obtains this composition.
Production Example 6: operation (1)
In the Production Example 5, replace Tetra hydro Phthalic anhydride 11.2g and use Tetra hydro Phthalic anhydride 22.3g, in addition, similarly implement with Production Example 5, obtain this composition.
[table 4]
Embodiment 13
＜operation (2) step 1 〉
Use Banbury (the smart machine-processed 600mL Labo Plasto Mill of Japan), cooperate this composition 2 mass parts that obtain in natural rubber (RSS#1) 100 mass parts, carbon black (N330) 45 mass parts, aqueous silicon dioxide (Nipsil AQ) 10 mass parts, stearic acid 3 mass parts, zinc oxide 5 mass parts and the Production Example 3 and carry out mixingly, obtain composition.
＜operation (2) step 2 〉
Utilize mill, cooperate composition, the vulcanization accelerator (N that obtains by operation (2) step 1 down at 60～80 ℃, N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine) 0.7 mass parts, insoluble sulphur 6 mass parts (as the sulphur composition) and cobalt naphthenate 2 mass parts and carry out mixingly obtain this rubber combination.
＜operation (3) 〉
By under 150 ℃, making this rubber combination sulfuration that obtains in operation (2) step 2, thereby obtain vulcanized rubber.
Embodiment 14 and 15
Among the embodiment 13, replace this composition that obtains in the Production Example 3 and use this composition that obtains respectively in the Production Example 4,5, in addition, operation similarly to Example 13 obtains this rubber combination and vulcanized rubber.
Comparative example 1
Among the embodiment 13, replace this composition that obtains in the Production Example 3 and use the aniline and the condensation reaction products of acetone that obtains in the Production Example 2, in addition, operate similarly to Example 13, obtain rubber combination and vulcanized rubber.
Comparative example 2
Among the embodiment 13, replace this composition that obtains in the Production Example 3 and use this composition that obtains in the Production Example 6, in addition, operation similarly to Example 13 obtains rubber combination and vulcanized rubber.
Test example 13～15, comparison test example 1,2
For the rubber combination and the vulcanized rubber that obtain respectively in embodiment 13～15, the comparative example 1,2, implement following oven test.
Oven test: use the test film according to No. 3, the dumbbell of JIS K6251, by JIS K6257B-1 method, 100 ℃ of oven tests of implementing 48 hours down.Test film after the use oven test, elongation (EB) when measuring cut-out by JIS K6251.Illustrate will use the rubber combination that obtains in the comparative example 1 and vulcanized rubber and value be made as 100 o'clock relative EB.
[table 5]
| ? | Relative EB |
| Test example 13 | 117 |
| Test example 14 | 128 |
| Test example 15 | 117 |
| Comparison test example 1 | 100 |
| Comparison test example 2 | 96 |
EB is more big relatively, we can say that then thermotolerance is more excellent.Therefore, if use this composition, then can improve the thermotolerance that the vulcanized rubber for the manufacturing of tire has more easily.
Utilizability on the industry
According to the present invention, can make primary amine content more easily and be the composition that contains 2,2,4 trimethyl 1,2 dihydroquinoline polymer below the 1 quality % for the total amount of composition.The composition that contains 2,2,4 trimethyl 1,2 dihydroquinoline polymer is useful as the tire antiaging agent.Be below the 1 quality % for the total amount of described composition by primary amine content, thereby the sulphur in the rubber composition for tire is difficult for being present on ground partially the rubber combination surface, its result exists to obtain the such advantage of sufficient cure efficiency easily in rubber combination inside.
In addition, according to the present invention, the stable on heating method that the vulcanized rubber that can provide improvement more easily to be used for the manufacturing of tire has.
Claims (15)
1. a primary amine content is to contain 2 below the 1 quality % for the total amount of composition, 2,4-trimethylammonium-1, the manufacture method of the composition of 2-dihydroquinoline polymkeric substance, it comprises: make to comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and the operation that contacts with the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine with respect to the mixture that for their total 100 mass parts is the primary amine of 2～6 mass parts.
2. manufacture method according to claim 1, it comprises:
Make acetone and aniline reaction, obtain comprising 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and be the operation of mixture of the primary amine of 2～6 mass parts for their total 100 mass parts; And
The operation that the mixture that makes gained contacts with the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine.
3. one kind contains 2,2,4-trimethylammonium-1, the composition of 2-dihydroquinoline polymkeric substance, it is characterized in that, be to contain 2,2,4-trimethylammonium-1 by what claim 1 or 2 described manufacture method obtained, the composition of 2-dihydroquinoline polymkeric substance, wherein, when obtaining forming composition by following preparation method, be below 0.5% 100 ℃ of following optical transmission rates with this forming composition insulation 600nm after 1 hour;
The preparation method of described forming composition is:
Contain composition 2 mass parts and insoluble sulphur 2 mass parts of 2,2,4 trimethyl 1,2 dihydroquinoline polymer by in divinyl rubber 100 mass parts, cooperating, thereby obtain title complex, prepare the thick forming composition of 2mm by this title complex.
4. rubber combination, it is by for crude rubber 100 mass parts in being selected from natural rubber and diene series rubber, cooperate insoluble sulphur 2～10 mass parts and contain 2 by what claim 1 or 2 described manufacture method obtained, 2,4-trimethylammonium-1, composition 0.5～5 mass parts of 2-dihydroquinoline polymkeric substance and obtaining.
5. the composition that contains 2,2,4 trimethyl 1,2 dihydroquinoline polymer that obtains by claim 1 or 2 described manufacture method is as the ageing-resistant purposes of tire.
6. the composition that the condensation reaction products of aniline and acetone and carboxylic acid anhydride is mixed and obtain is used for improving the stable on heating purposes that vulcanized rubber has.
7. comprise following operation (1), (2) and stable on heating improvement method (3), that vulcanized rubber has;
(1) make and comprise 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof and the operation that contacts with the carboxylic acid anhydride that is 3～10 moles for 1 mole of this primary amine with respect to the mixture that for their total 100 mass parts is the primary amine of 2～6 mass parts,
(2) mixture, rubber constituent and the sulphur composition that obtains in the operation (1) carried out mixing operation,
(3) make the mixing thing sulfuration that obtains in the operation (2) and the operation that obtains vulcanized rubber.
8. improvement method according to claim 7, wherein,
Operation (1) is implemented under the condition that does not have rubber constituent.
9. according to claim 7 or 8 described improvement methods, wherein,
Operation (1) is implemented under the condition that does not have the sulphur composition.
10. according to each described improvement method in the claim 7～9, wherein,
The usage quantity of the carboxylic acid anhydride in the operation (1) is 0.6～5 mole for the condensation reaction products 1kg of aniline and acetone.
11. a vulcanized rubber improved heat resistance agent, it obtains by the condensation reaction products of aniline and acetone and carboxylic acid anhydride are mixed.
12. vulcanized rubber according to claim 11 improved heat resistance agent, wherein,
The condensation reaction products of aniline and acetone is for comprising 2,2,4-trimethylammonium-1,2-dihydroquinoline, 2,2,4-trimethylammonium-1, the polymkeric substance of 2-dihydroquinoline, and the mixture of primary amine.
13. according to claim 11 or 12 described vulcanized rubber improved heat resistance agent, wherein,
The condensation reaction products of aniline and acetone is for comprising 2,2,4-trimethylammonium-1,2-dihydroquinoline, 2,2,4-trimethylammonium-1, the polymkeric substance of 2-dihydroquinoline and with respect to 2,2,4-trimethylammonium-1,2-dihydroquinoline and 2,2,4-trimethylammonium-1, total 100 mass parts of the polymkeric substance of 2-dihydroquinoline are the mixture of the primary amine of 2～6 mass parts.
14. according to claim 12 or 13 described vulcanized rubber improved heat resistance agent, it is by being that 3～10 moles carboxylic acid anhydride mixes and gets with the condensation reaction products of aniline and acetone with for 1 mole of the contained primary amine of aniline and the condensation reaction products of acetone.
15. according to each described vulcanized rubber improved heat resistance agent in the claim 11～14, wherein,
The condensation reaction products of aniline and acetone is for by making aniline and acetone carry out the product that condensation reaction produces under the condition that does not have the sulphur composition.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010233302 | 2010-10-18 | ||
| JP2010-233302 | 2010-10-18 | ||
| JP2011047440 | 2011-03-04 | ||
| JP2011-047440 | 2011-03-04 | ||
| PCT/JP2011/074094 WO2012053572A1 (en) | 2010-10-18 | 2011-10-13 | Method for producing 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing compositions |
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| CN2011800609512A Pending CN103261166A (en) | 2010-10-18 | 2011-10-13 | Method for producing 2,2,4-trimethyl-1,2-dihydroquinoline polymer-containing compositions |
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| JP (2) | JP2012197415A (en) |
| CN (1) | CN103261166A (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110099802A (en) * | 2016-12-20 | 2019-08-06 | 米其林集团总公司 | Rubber composition comprising specific rubber powder |
| CN114315712A (en) * | 2020-09-27 | 2022-04-12 | 中石化南京化工研究院有限公司 | Method for purifying 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103694169B (en) * | 2012-09-28 | 2016-04-06 | 中国石油化工股份有限公司 | Micro passage reaction is utilized to synthesize the method for 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof |
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| CA1107053A (en) * | 1977-07-22 | 1981-08-18 | Tadashi Watanabe | Antioxidant for rubber |
| JPS58126868A (en) * | 1982-01-25 | 1983-07-28 | Sumitomo Chem Co Ltd | Purification of 2,2,4-trimethyl-1,2-dihydroquinoline |
| US4897482A (en) * | 1988-06-10 | 1990-01-30 | Bayer Aktiengesellschaft | Process for the preparation of oligomeric 2,2,4-trimethyl-1,2-dihydroquinoline |
| CN1093724A (en) * | 1993-02-03 | 1994-10-19 | 住友化学工业株式会社 | Reinforcing rubber articles, its production method and suitable rubber combination |
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| JP3275418B2 (en) * | 1993-02-03 | 2002-04-15 | 住友化学工業株式会社 | Rubber product reinforced with organic fiber and method for producing the same |
| JP3275419B2 (en) * | 1993-02-03 | 2002-04-15 | 住友化学工業株式会社 | Rubber composition and method of bonding to steel cord using the same |
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2011
- 2011-10-12 JP JP2011224675A patent/JP2012197415A/en active Pending
- 2011-10-12 JP JP2011224676A patent/JP2012197416A/en active Pending
- 2011-10-13 CN CN2011800609512A patent/CN103261166A/en active Pending
- 2011-10-13 WO PCT/JP2011/074094 patent/WO2012053572A1/en active Application Filing
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|---|---|---|---|---|
| CA1107053A (en) * | 1977-07-22 | 1981-08-18 | Tadashi Watanabe | Antioxidant for rubber |
| JPS58126868A (en) * | 1982-01-25 | 1983-07-28 | Sumitomo Chem Co Ltd | Purification of 2,2,4-trimethyl-1,2-dihydroquinoline |
| US4897482A (en) * | 1988-06-10 | 1990-01-30 | Bayer Aktiengesellschaft | Process for the preparation of oligomeric 2,2,4-trimethyl-1,2-dihydroquinoline |
| CN1093724A (en) * | 1993-02-03 | 1994-10-19 | 住友化学工业株式会社 | Reinforcing rubber articles, its production method and suitable rubber combination |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110099802A (en) * | 2016-12-20 | 2019-08-06 | 米其林集团总公司 | Rubber composition comprising specific rubber powder |
| CN110099802B (en) * | 2016-12-20 | 2021-04-02 | 米其林集团总公司 | Rubber composition comprising specific rubber powder |
| CN114315712A (en) * | 2020-09-27 | 2022-04-12 | 中石化南京化工研究院有限公司 | Method for purifying 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer |
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| JP2012197416A (en) | 2012-10-18 |
| JP2012197415A (en) | 2012-10-18 |
| WO2012053572A1 (en) | 2012-04-26 |
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