CN108034077B - A kind of additive introducing rubber composition and its preparation and application - Google Patents
A kind of additive introducing rubber composition and its preparation and application Download PDFInfo
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- CN108034077B CN108034077B CN201711346769.9A CN201711346769A CN108034077B CN 108034077 B CN108034077 B CN 108034077B CN 201711346769 A CN201711346769 A CN 201711346769A CN 108034077 B CN108034077 B CN 108034077B
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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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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Abstract
The present invention relates to a kind of additive that can introduce rubber composition and its preparation and application, chemical structural formulas are as follows:.Wherein, n is the oxidation state of metal M, numerical value 2,3 or 4；A is one of oxygen, sulphur, carbon, nitrogen, phosphorus or silicon, 0≤x≤10；B is one of oxygen, sulphur, carbon, nitrogen, phosphorus or silicon, (AxBy)mIndicate that atom is connected with chemical bond, 0≤y≤10；A, B is not same element, and x and y do not take 0 simultaneously；0≤m≤10；z≤50；R1And R2For the aliphatic chain, alicyclic or aromatic compound of carbon atom number 0 to 50；R3, R4For the aliphatic chain or alicyclic of carbon atom number 0 to 50；A and b is positive integer.Additive of the invention can introduce rubber composition, the hardness of synthesis improvement rubber, wet-sliding resistant performance, dynamic mechanical and tensile property, even in few examples, these rubber compositions for containing above-mentioned rubber additive all have the shore hardness of raising, elongation at break and wet-sliding resistant performance.
Description
Technical field
The present invention relates to rubber for tire additive agent field, more particularly, to one kind can introduce rubber composition additive and
It is prepared and application.
Background technique
Wet-sliding resistant performance is an important indicator of tire.Automobile is in the road traveling for having water, due to the presence of water, wheel
The road holding of tire can sharp fall.This not only influences the tractive force of automobile, but will influence system of the automobile in emergency brake
Dynamic distance, influences the safety driven.Therefore, anti-slippery is the important finger for measuring tire wet traction and driving safety
Mark.But existing rubber additive is difficult not when modified to the rubber compositions product such as such as tire progress wet-sliding resistant performance
Influence the otherwise performance of such as hardness, dynamic mechanical of product, that is to say, that existing rubber additive is more difficult
To reach the more excellent modification of synthesis to the anti-slippery modification of rubber composition.The application is based on the proposition of this problem.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind can introduce rubber group
The additive of conjunction object and its preparation and application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of additive introducing rubber composition, chemical structural formula are as follows:
Wherein, n is the oxidation state of metallic element M, n=2,3 or 4；A is one of following atom: oxygen, sulphur, carbon, nitrogen,
Phosphorus, silicon, 0≤x≤10；B is one of following atom: oxygen, sulphur, carbon, nitrogen, phosphorus, silicon, 0≤y≤10；X and y do not take 0 simultaneously；
(AxBy)mIndicate that atom is connected with chemical bond, 0≤m≤10；z≤50)；R1And R2Aliphatic chain, alicyclic ring for carbon atom number 0 to 50
Hydrocarbon or aromatic compound；R3, R4For the saturation or unsaturated fatty chain or alicyclic of carbon atom number 0 to 50；A and b is positive integer.
(OH)a-R3- COOH indicates that hydroxyl (- OH) can connect in R3On, and at least one hydroxyl is connected to R3On.
(OH)b-R4- COOH indicates that hydroxyl (- OH) can connect in R4On, and at least one hydroxyl is connected to R4On.
The aromatic cycle compound is benzene, phenyl ring polymer or heterocyclic compound as a preferred embodiment of the above solution,.It is common
Phenyl ring polymer have naphthalene, anthracene etc., can also be the structures such as fullerene or graphene；Cyclization is organized among the heterocyclic compound
Atom not only include carbon, further include the atoms such as nitrogen, oxygen or sulphur；For example, common nitrogen-containing heterocycle compound have pyrroles, pyridine,
Quinoline, pyrazoles, imidazoles, 1,2,3- triazole, 1,2,4- triazole, tetrazolium, oxazole, isoxazole, thiazole, benzimidazole, benzotriazole,
Benzoxazoles, benzothiazole, 2-methylimidazole, 3- picoline or 3- methylpyrazole.
Preferably, R3And R4On hydroxyl be primary hydroxyl, secondary hydroxyl and tert-hydroxyl；It is furthermore preferred that R3And R4On hydroxyl be
Secondary hydroxyl and tert-hydroxyl；It is furthermore preferred that R3And R4On hydroxyl be secondary hydroxyl.
Preferably, R3And R4On unsaturated bond be double bond；It is furthermore preferred that R3And R4On unsaturated bond be carbon-carbon double bond,
Double bond is to be conjugated or isolated formal distribution is on aliphatic chain.
Preferably, the metal M is selected from one of following metallic element:
The metal of the metal of I B to VIII B race or II A to VI A race in the periodic table of elements；It is furthermore preferred that the metal M is selected
From one of calcium, iron, magnesium, titanium, aluminium or vanadium；Even more preferably, the metal M is selected from calcium, one of magnesium and aluminium.
A kind of preparation method for the additive introducing rubber composition, comprising the following steps:
(1) double carboxylic bronsted lowry acids and bases bronsted lowries are taken, or the salt of double carboxylic acids is directly taken to be placed in polar solvent, are heated, until solution is completely saturating
It is bright, obtain double carboxylic acid salt solution A；
(2) band alcoholic extract hydroxyl group aliphatic carboxylic acid and alkali are taken, or directly to take the salt with alcoholic extract hydroxyl group aliphatic carboxylic acid to be placed in polarity molten
In agent, heating obtains band alcoholic extract hydroxyl group aliphatic carboxylate solution B until solution is fully transparent；
(3) under agitation, mix double carboxylic acid salt solution A, band alcoholic extract hydroxyl group aliphatic carboxylate solution B with it is configured
Metal M salting liquid, reaction obtain solid product, filter, washing, dry to get arriving purpose product rubber additive；
For example, the structural formula of double carboxylic acids are as follows: HOOC-R1-(AxBy)m-R2-COOH；
For example, the structural formula with alcoholic extract hydroxyl group aliphatic carboxylic acid are as follows: (OH)a-R3- COOH or (OH)b-R4-COOH。
Preferably, the salt with phenolic hydroxyl group aromatic carboxylic acid in solution B is a kind of salt with phenolic hydroxyl group aromatic carboxylic acid or more
Kind has the salt of the phenolic hydroxyl group aromatic carboxylic acid of different structure according to the substance obtained after the mixing of any ratio；
Double carboxylate products are to meet structural formula HOOC-R in double carboxylic acid salt solution A1-(AxBy)mOne kind of-R2-COOH or
The salt product of a variety of double carboxylic acids.
The order by merging of the solution A, solution B and metal M salting liquid can specifically: solution A is taken, under agitation,
Metal M salting liquid is poured into, solution C is obtained, under agitation, pours into solution B to solution C, reaction is obtained into solid product, mistake
Filter, washing are dried to get purpose product additive is arrived.It is of course also possible to be not limited to foregoing description, mixed with random order, only
It wants that final solid product can be obtained.
The metal M salt can be anhydrous calcium chloride, Potassium aluminum sulfate dodecahydrate, aluminum sulfate, alchlor, anhydrous chlorination
It is magnesium, magnesium sulfate, ferric trichloride, titanium tetrachloride, titanium sulfate, a kind of in vanadium trichloride.
The alkali is selected from sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate or ammonium hydroxide as a preferred embodiment of the above solution,
One of；
The polar solvent be selected from water, tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, acetic acid,
It is a kind of in n-butanol, isopropanol, propyl alcohol, ethyl alcohol or methanol；
The structural formula of double carboxylic acids described in step (1) as a preferred embodiment of the above solution, are as follows: HOOC-R1-(AxBy)m-R2-
The preferred nitrogen of COOH, A and B, oxygen, sulphur；Preferred A and B is sulphur；
Described in step (2) band alcoholic extract hydroxyl group aliphatic carboxylic acid be selected from jalapinolic acid, 16- hydroxyl Heptadecanoic acide,
12- hydroxyoctadecanoic acid, 6- hydroxyl nonadecylic acid, 11- hydroxyeicosanoic acid, 2- hydroxyl carboceric acid, 9,18- dihydroxy ten
Eight alkanoic acids, 11,18- dihydroxy octadecanoid acid, 8,19- dihydroxy nonadecylic acid, 9,19- dihydroxy nonadecylic acid, the 10- hydroxyl last of the ten Heavenly stems
One of sour, trans- 10-HAD decylenic acid or gluconic acid.
As the preferred of above-mentioned addictive preparation method,
The molar ratio of the double carboxylic acids and alkali that add in step (1) is (1~2): 2, concentration of the alkali in polar solvent is 0.2
~0.4mol/L heats the process conditions of reaction are as follows: is heated to 90 DEG C and is vigorously stirred 1h；
The band alcoholic extract hydroxyl group aliphatic carboxylic acid added in step (2) is single substance, and the molar ratio with alkali is (1~2): 2, or
Directly add a kind of salt with alcoholic extract hydroxyl group aliphatic carboxylic acid in person's step (2), concentration of the alkali in polar solvent is 0.2~
0.4mol/L heats the process conditions of reaction are as follows: is heated to 90 DEG C and is vigorously stirred 1h；；
In step (3): for solution A, solution B and metal M salting liquid, preferred order by merging is that solution A pours into metal
M salting liquid obtains solution C, and solution B pours into A again, and the concentration of metal M salting liquid is 0.30~0.50mol/L, drying after washing
Process conditions are as follows: continue vacuum drying 12 hours after being first dried in vacuo 12 hours at 90 DEG C at 110 DEG C again.
In step (3): the volume ratio of the additive amount of solution A, solution B and metal M salting liquid three is (0.8~1.2):
(1.6~2.4): 2, solution A pours into the speed of metal M salting liquid and pours into the 1% of total solution A volume to be per second, and solution B is fallen
Enter the speed of C and pours into the 1% of total solution B volume to be per second.
A kind of additive introducing rubber composition is preparing rubber for tire, sole rubber, yielding rubber, coating, glue
Application in stick or chemical product.
When the rubber additive is prepared for rubber for tire as a preferred embodiment of the above solution, the rubber of every 100 parts by weight
1~200 part of metallic soap (rubber additive) is added in matrix, other additives of rubber product are using in traditional rubber
The type and additive amount of additive.
When the rubber additive is prepared for rubber for tire, sole rubber or yielding rubber, corresponding applicable rubber
Matrix is thermoplastic elastomer (TPE) or foaming elastomer, the specially butadiene-styrene rubber, nitrile rubber of thermoplasticity or foaming, natural rubber
Glue, organic silicon rubber, polyurethane rubber or isopropyl rubber etc.；
When the rubber additive is used for coating preparation, corresponding applicable coating is acrylic compounds, polyurethanes, polyethers
Class or epoxy resin coating etc.；
When the rubber additive is prepared for adhesive, the base-material of corresponding applicable adhesive is natural material, closes
At high molecular material and inorganic material；
When the rubber additive is prepared for chemical product, corresponding applicable chemical product be cosmetics, fragrance, soap or
Toothpaste etc..
Following inference is without being bound by any theory: on the one hand, when additive produced by the present invention is used to prepare rubber,
R3, R4Fat chain structure in group can be tangled with rubber molecule to react, R3, R4The alcoholic extract hydroxyl group of upper connection being capable of affine rubber
The groups containing oxygen atom such as the hydroxyl on the common reinforced filling of glue (such as carbon black, white carbon black) surface, so as to reduce rubber
The generation of the middle three-dimensional netted mechanism of filler, is conducive to filler and disperses in rubber mass；On the other hand, addition produced by the present invention
When agent is used to prepare rubber, in the additive-(AxBy)mAtom in group is connected with chemical bond, in the vulcanization of rubber
Key fracture (bond cleavage) can occur under curing temperature and generate free radicals, these free radicals for Cheng Zhong, above-mentioned chemical bond
It can be chemically reacted with the double bond in rubber mass, the additive is helped to be connected on rubber mass strand；Upper
Under effect of both stating, when additive produced by the present invention is used to prepare rubber, can synthesis improvement rubber hardness, it is anti-slippery
Performance, dynamic mechanical and tensile property.
Compared with prior art, additive preparation process of the invention is simple, and each component raw material is easy to get, and is suitable for industrializing
Production；Additive for rubber system for when, solubility in rubber mass is high.From the exemplary reality in specific embodiment
Example is applied it is found that additive of the invention is used in the rubber compoundings such as diene rubber, it can be anti-slippery with the hardness of synthesis improvement rubber
Performance, dynamic mechanical and tensile property.
Specific embodiment
A kind of additive introducing rubber composition, chemical structural formula are as follows:
Wherein, n is the oxidation state of metallic element M, n=2,3 or 4；A is one of following atom: oxygen, sulphur, carbon, nitrogen,
Phosphorus, silicon, 0≤x≤10；B is one of following atom: oxygen, sulphur, carbon, nitrogen, phosphorus, silicon, 0≤y≤10；X and y do not take 0 simultaneously；
(AxBy)mIndicate that atom is connected with chemical bond, 0≤m≤10；z≤50)；R1And R2Aliphatic chain, alicyclic ring for carbon atom number 0 to 50
Hydrocarbon or aromatic compound；R3, R4For the saturation or unsaturated fatty chain or alicyclic of carbon atom number 0 to 50；A and b is positive integer.
(OH)a-R3- COOH indicates that hydroxyl (- OH) can connect in R3On, and at least one hydroxyl is connected to R3On.
(OH)b-R4- COOH indicates that hydroxyl (- OH) can connect in R4On, and at least one hydroxyl is connected to R4On.
As the preferred embodiment of above scheme, the aromatic cycle compound is benzene, phenyl ring polymer or heterocycle
Compound.Common phenyl ring polymer has naphthalene, anthracene etc., can also be the structures such as fullerene or graphene；The heterocyclic compound
The atom that cyclization is organized among object not only includes carbon, further includes the atoms such as nitrogen, oxygen or sulphur；For example, common nitrogen-containing heterocycle compound
There are pyrroles, pyridine, quinoline, pyrazoles, imidazoles, 1,2,3- triazole, 1,2,4- triazole, tetrazolium, oxazole, isoxazole, thiazole, benzo miaow
Azoles, benzotriazole, benzoxazoles, benzothiazole, 2-methylimidazole, 3- picoline or 3- methylpyrazole.
As the preferred embodiment of above scheme, R3And R4On hydroxyl be primary hydroxyl, secondary hydroxyl and tert-hydroxyl；More
Preferably, R3And R4On hydroxyl be secondary hydroxyl and tert-hydroxyl；It is furthermore preferred that R3And R4On hydroxyl be secondary hydroxyl.
As the preferred embodiment of above scheme, R3And R4On unsaturated bond be double bond；It is furthermore preferred that R3And R4
On unsaturated bond be carbon-carbon double bond, double bond is to be conjugated or isolated formal distribution is on aliphatic chain.
As the preferred embodiment of above scheme, the metal M is selected from one of following metallic element:
The metal of the metal of I B to VIII B race or II A to VI A race in the periodic table of elements；It is furthermore preferred that the metal M is selected
From one of calcium, iron, magnesium, titanium, aluminium or vanadium；Even more preferably, the metal M is selected from calcium, one of magnesium and aluminium.
A kind of preparation method for the additive introducing rubber composition, comprising the following steps:
(1) double carboxylic bronsted lowry acids and bases bronsted lowries are taken, or the salt of double carboxylic acids is directly taken to be placed in polar solvent, are heated, until solution is completely saturating
It is bright, obtain double carboxylic acid salt solution A；
(2) band alcoholic extract hydroxyl group aliphatic carboxylic acid and alkali are taken, or directly to take the salt with alcoholic extract hydroxyl group aliphatic carboxylic acid to be placed in polarity molten
In agent, heating obtains band alcoholic extract hydroxyl group aliphatic carboxylate solution B until solution is fully transparent；
(3) under agitation, mix double carboxylic acid salt solution A, band alcoholic extract hydroxyl group aliphatic carboxylate solution B with it is configured
Metal M salting liquid, reaction obtain solid product, filter, washing, dry to get arriving purpose product rubber additive；
For example, the structural formula of double carboxylic acids are as follows: HOOC-R1-(AxBy)m-R2-COOH；
For example, the structural formula with alcoholic extract hydroxyl group aliphatic carboxylic acid are as follows: (OH)a-R3- COOH or (OH)b-R4-COOH。
As the preferred embodiment of above scheme, the salt with phenolic hydroxyl group aromatic carboxylic acid in solution B is a kind of band phenol
After the salt of the salt of hydroxy aromatic carboxylic acids or a variety of phenolic hydroxyl group aromatic carboxylic acids with different structure is mixed according to any ratio
Obtained substance；
Double carboxylate products are to meet structural formula HOOC-R in double carboxylic acid salt solution A1-(AxBy)m-R2One kind of-COOH or
The salt product of a variety of double carboxylic acids.
The order by merging of the solution A, solution B and metal M salting liquid can specifically: solution A is taken, under agitation,
Metal M salting liquid is poured into, solution C is obtained, under agitation, pours into solution B to solution C, reaction is obtained into solid product, mistake
Filter, washing are dried to get purpose product additive is arrived.It is of course also possible to be not limited to foregoing description, mixed with random order, only
It wants that final solid product can be obtained.
The metal M salt can be anhydrous calcium chloride, Potassium aluminum sulfate dodecahydrate, aluminum sulfate, alchlor, anhydrous chlorination
It is magnesium, magnesium sulfate, ferric trichloride, titanium tetrachloride, titanium sulfate, a kind of in vanadium trichloride.
As the preferred embodiment of above scheme, the alkali is selected from sodium hydroxide, potassium hydroxide, potassium carbonate, carbon
One of sour sodium or ammonium hydroxide；
The polar solvent be selected from water, tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, acetic acid,
It is a kind of in n-butanol, isopropanol, propyl alcohol, ethyl alcohol or methanol；
As the preferred embodiment of above scheme, the structural formula of double carboxylic acids described in step (1) are as follows: HOOC-R1-
(AxBy)m-R2The preferred nitrogen of-COOH, A and B, oxygen, sulphur；Preferred A and B is sulphur；
Described in step (2) band alcoholic extract hydroxyl group aliphatic carboxylic acid be selected from jalapinolic acid, 16- hydroxyl Heptadecanoic acide,
12- hydroxyoctadecanoic acid, 6- hydroxyl nonadecylic acid, 11- hydroxyeicosanoic acid, 2- hydroxyl carboceric acid, 9,18- dihydroxy ten
Eight alkanoic acids, 11,18- dihydroxy octadecanoid acid, 8,19- dihydroxy nonadecylic acid, 9,19- dihydroxy nonadecylic acid, the 10- hydroxyl last of the ten Heavenly stems
One of sour, trans- 10-HAD decylenic acid or gluconic acid.
As the preferred embodiment of above-mentioned addictive preparation method,
The molar ratio of the double carboxylic acids and alkali that add in step (1) is (1~2): 2, concentration of the alkali in polar solvent is 0.2
~0.4mol/L heats the process conditions of reaction are as follows: is heated to 90 DEG C and is vigorously stirred 1h；
The band alcoholic extract hydroxyl group aliphatic carboxylic acid added in step (2) is single substance, and the molar ratio with alkali is (1~2): 2, or
Directly add a kind of salt with alcoholic extract hydroxyl group aliphatic carboxylic acid in person's step (2), concentration of the alkali in polar solvent is 0.2~
0.4mol/L heats the process conditions of reaction are as follows: is heated to 90 DEG C and is vigorously stirred 1h；；
In step (3): for solution A, solution B and metal M salting liquid, preferred order by merging is that solution A pours into metal
M salting liquid obtains solution C, and solution B pours into A again, and the concentration of metal M salting liquid is 0.30~0.50mol/L, drying after washing
Process conditions are as follows: continue vacuum drying 12 hours after being first dried in vacuo 12 hours at 90 DEG C at 110 DEG C again.
In step (3): the volume ratio of the additive amount of solution A, solution B and metal M salting liquid three is (0.8~1.2):
(1.6~2.4): 2, solution A pours into the speed of metal M salting liquid and pours into the 1% of total solution A volume to be per second, and solution B is fallen
Enter the speed of C and pours into the 1% of total solution B volume to be per second.
A kind of additive introducing rubber composition is preparing rubber for tire, sole rubber, yielding rubber, coating, glue
Application in stick or chemical product.
As the preferred embodiment of above scheme, when the rubber additive is prepared for rubber for tire, every 100 weight
The metallic soap (rubber additive) in the rubber mass of part added with 1~200 part is measured, other additives of rubber product are using normal
Advise the type and additive amount of the additive in rubber.
When the rubber additive is prepared for rubber for tire, sole rubber or yielding rubber, corresponding applicable rubber
Matrix is thermoplastic elastomer (TPE) or foaming elastomer, the specially butadiene-styrene rubber, nitrile rubber of thermoplasticity or foaming, natural rubber
Glue, organic silicon rubber, polyurethane rubber or isopropyl rubber etc.；
When the rubber additive is used for coating preparation, corresponding applicable coating is acrylic compounds, polyurethanes, polyethers
Class or epoxy resin coating etc.；
When the rubber additive is prepared for adhesive, the base-material of corresponding applicable adhesive is natural material, closes
At high molecular material and inorganic material；
When the rubber additive is prepared for chemical product, corresponding applicable chemical product be cosmetics, fragrance, soap or
Toothpaste etc..
The present invention is described in detail combined with specific embodiments below.
Embodiment 1
A kind of additive introducing rubber composition, chemical structural formula are as follows:
The preparation method of above-mentioned additive, comprising the following steps:
(1) 1L distilled water and 16g sodium hydrate solid (purity >=97%, purchased from me are added in the beaker of a 2L
Fourth).After sodium hydroxide is completely dissolved, 42.05g 3,3'- dithiodipropionic acid (purity >=99.0% (GC) (T), purchase is added
From TCI).Said mixture is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution A)
(2) 1L distilled water and 16g sodium hydrate solid (purity >=97%, purchased from me are added in the beaker of a 2L
Fourth).After sodium hydroxide is completely dissolved, 120.19g 12- hydroxy stearic acid is added (purity >=80% is purchased from TCI).It will be above-mentioned
Mixture is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution D)
(3) take the beaker of a 4L again, be added thereto 1L distilled water and 189.76g Potassium aluminum sulfate dodecahydrate (purity >=
99%, it is purchased from Aladdin).Said mixture is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution
B)
(4) then solution A is slowly poured into solution B with the speed of 10mL/s in the case where being vigorously stirred solution B,
Obtain solution C.
(5) then solution D is slowly poured into solution C with the speed of 10mL/s in the case where being vigorously stirred solution C,
Obtain white solid product.Resulting white solid product distillation washing 5 times will be filtered, vacuum drying oven 90 is then put it into
DEG C vacuum drying 12 hours after by oven temperature rise to 110 DEG C continue vacuum drying 12 hours.Final product be white powder (i.e.
For purpose product).
Embodiment 2
A kind of additive introducing rubber composition, chemical structural formula are as follows:
The preparation method of above-mentioned additive, comprising the following steps:
(1) 1L distilled water and 16g sodium hydrate solid (purity >=97%, purchased from me are added in the beaker of a 2L
Fourth).After sodium hydroxide is completely dissolved, 42.05g 3,3'- dithiodipropionic acid (purity >=99.0% (GC) (T), purchase is added
From TCI).Said mixture is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution A)
(2) (purity >=90% is purchased from for addition 1L distilled water and 128.18g sodium ricinoleate in the beaker of a 2L
TCI).Said mixture is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution D)
(3) take the beaker of a 4L again, be added thereto 1L distilled water and 189.76g Potassium aluminum sulfate dodecahydrate (purity >=
99%, it is purchased from Aladdin).Said mixture is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution
B)
(4) then solution A is slowly poured into solution B with the speed of 10mL/s in the case where being vigorously stirred solution B,
Obtain solution C.
(5) then solution D is slowly poured into solution C with the speed of 10mL/s in the case where being vigorously stirred solution C,
Obtain faint yellow solid product.Resulting faint yellow solid product distillation washing 5 times will be filtered, vacuum baking is then put it into
90 DEG C of case vacuum drying 12 hours after by oven temperature rise to 110 DEG C continue vacuum drying 12 hours.Final product is faint yellow
Blocks of solid (as purpose product).
Embodiment 3-5
With white carbon black be main reinforced filling rubber composition in be separately added into addition obtained by embodiment 1-2
Agent, wherein Rubber mix formulations are as shown in table 1.Blank control Rubber mix formulations are as shown in embodiment 3 in table 1, in reality
Applying joined the product obtained of embodiment 1 in the rubber composition of example 4, joined implementation in the rubber composition of embodiment 5
The product obtained of example 2.The specific mixing step of filler, auxiliary agent, vulcanizing agent etc. is listed in Table 2 in embodiment 3-5.Embodiment 1-
2 product is added simultaneously with reinforced filling.Rubber composition after mixing slice on a mill, then with vulcanizing press into
Row solidification, solidification temperature be 150 DEG C, curing time be 30 minutes to get arrive rubber sample.
The formula table of 1 embodiment 3-5 of table
2 compounding conditions table of table
To rubber sample made from embodiment 3-5 carry out solidified sample hardness, extension test, dynamic mechanical test with
And wet and slippery test, detection data are listed in Table 3 below.From the data of table 3 it can be seen that the rubber that white carbon black is main reinforced filling mixes
It closes in object, blank sample is compared with the rubber sample for being added to embodiment 1, embodiment 2, after additive described in addition 10Phr
Sample all there is the shore hardness of raising, elongation at break, and the anti-slippery characterized with mono-pendulum type friction coefficient tester
Energy；Sample after additive described in part addition 10Phr has the breaking strength and elongation at break product improved；For institute
There is the sample after additive described in addition 10Phr, the storage modulus at 60 DEG C is declined slightly, and the fissipation factor at 60 DEG C has not
With the raising of degree.
The test data table of the rubber sample of 3 embodiment 3-5 of table
Above-mentioned extension test is carried out according to standard ASTM-D412, and environment temperature is 25 DEG C when test.Test sample is ring
Shape, ring internal diameter 14.0mm, ring outer diameter 16.0mm, height 3.00mm.
Anton Paar EC302 rheometer is used to measure the dynamic mechanical of solidified sample.Dynamic mechanical test sample
It is also ring-type, size is essentially identical with Tensile test specimens.Test condition are as follows: under 60 DEG C, 0.5 hertz of frequency strain from
0.001% to 15% strain sweep.
Embodiment 6
A kind of preparation method of additive, comprising the following steps:
(1) be added in the beaker of a 2L 1L distilled water and 0.4mol sodium hydrate solid (purity >=97%, purchased from Ah
Latin).After sodium hydroxide is completely dissolved, addition 0.2mol 3,3'- dithiodipropionic acid (purity >=99.0% (GC) (T),
Purchased from TCI).Said mixture is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution A)
(2) be added in the beaker of a 2L 1L distilled water and 0.4mol sodium hydrate solid (purity >=97%, purchased from Ah
Latin).After sodium hydroxide is completely dissolved, 0.4mol 10- hydroxydecanoic acid (96%, be purchased from Sigma) is added.By above-mentioned mixing
Object is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution D)
(3) take the beaker of a 4L again, be added thereto 1L distilled water and 0.4mol Potassium aluminum sulfate dodecahydrate (purity >=
99%, it is purchased from Aladdin).Said mixture is heated to 90 DEG C and is vigorously stirred 1 hour, until solution is fully transparent.(solution
B)
(4) then solution A is slowly poured into solution B with the speed of 10mL/s in the case where being vigorously stirred solution B,
Obtain solution C.
(5) then solution D is slowly poured into solution C with the speed of 10mL/s in the case where being vigorously stirred solution C,
Obtain white solid product.Resulting white solid product distillation washing 5 times will be filtered, vacuum drying oven 90 is then put it into
DEG C vacuum drying 12 hours after by oven temperature rise to 110 DEG C continue vacuum drying 12 hours.Final product be white powder (i.e.
For purpose product).
Embodiment 7
In addition to the additional amount of sodium hydroxide in step (1) is changed to 0.30mol, the additional amount of 3,3'- dithiodipropionic acids changes
For 0.15mol；The additional amount of sodium hydroxide is changed to 0.30mol in step (2), and the additional amount of 10- hydroxydecanoic acid is changed to
0.30mol；The additional amount of Potassium aluminum sulfate dodecahydrate is changed to outside 0.30mol in step (3), remaining is in the same manner as in Example 6.
Embodiment 8
In addition to the additional amount of sodium hydroxide in step (1) is changed to 0.2mol, the additional amount of 3,3'- dithiodipropionic acids is changed to
0.1mol；The additional amount of sodium hydroxide is changed to 0.2mol in step (2), and the additional amount of 10- hydroxydecanoic acid is changed to 0.1mol；Step
(3) additional amount of Potassium aluminum sulfate dodecahydrate is changed to outside 0.20mol in, remaining is in the same manner as in Example 6.
Embodiment 9-11
With white carbon black be main reinforced filling rubber composition in be separately added into metal obtained by embodiment 6-8
Soap obtains the Rubber mix formulations such as embodiment 9-11, can specifically be shown in Table 4 the (correspondence of embodiment 9
Embodiment 6, and so on).
The formula table of 4 embodiment 9-11 of table
The mixing of such as 2 compounding conditions of table is carried out according to above-mentioned formula to get rubber sample is arrived.
Embodiment 12-23
Compared with Example 6, the overwhelming majority is all identical, in addition to the present embodiment is corresponding by the 10- hydroxydecanoic acid in step (2)
Jalapinolic acid, the 16- hydroxyl Heptadecanoic acide of equimolar amounts, 12- hydroxyoctadecanoic acid, 6- hydroxyl ten are replaced with respectively
Nine alkanoic acids, 11- hydroxyeicosanoic acid, 2- hydroxyl carboceric acid, 9,18- dihydroxy octadecanoid acid, 11,18- dihydroxy 18
Alkanoic acid, 8,19- dihydroxy nonadecylic acid, 9,19- dihydroxy nonadecylic acid, trans- 10-HAD decylenic acid or gluconic acid.
Embodiment 24-27
Compared with Example 6, the overwhelming majority is all identical, rubs in addition to the present embodiment accordingly replaces with sodium hydroxide etc. respectively
Potassium hydroxide, potassium carbonate, sodium carbonate or the ammonium hydroxide of your amount.
Embodiment 28-38
Compared with Example 6, the overwhelming majority is all identical, in addition to the present embodiment accordingly replaces polar solvent distilled water respectively
For tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, acetic acid, n-butanol, isopropanol, propyl alcohol, ethyl alcohol or first
Alcohol.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. the additive that one kind can introduce rubber composition, which is characterized in that its chemical structural formula are as follows:
Wherein, n is the oxidation state of metal M, numerical value 2,3 or 4；
A is one of oxygen, sulphur, carbon or nitrogen, 0≤x≤10；
B is one of oxygen, sulphur, carbon or nitrogen, 0≤y≤10；
(AxBy)mIndicate that atom is connected with chemical bond, x and y do not take 0 simultaneously；
0≤m≤10；Z=1；
R1And R2For the aliphatic chain, alicyclic or aromatic compound of carbon atom number 0 to 50；
R3, R4For the saturation or unsaturated fatty chain or alicyclic of carbon atom number 0 to 50；
A and b is positive integer.
2. the additive that one kind according to claim 1 can introduce rubber composition, which is characterized in that the aromatization
Conjunction object is benzene, phenyl ring polymer or heterocyclic compound；
R3And R4On be respectively connected with hydroxyl.
3. the additive that one kind according to claim 1 can introduce rubber composition, which is characterized in that work as R3And R4In
When functional group includes double bond, number is at least one, and when double bond number is greater than 2, and double bond is to be conjugated or isolated form point
Cloth is on aliphatic chain.
4. the additive that one kind according to claim 1 can introduce rubber composition, which is characterized in that the metal M
Selected from one of following metallic element:
The metal of the metal of I B to VIII B race or II A to VI A race in the periodic table of elements.
5. the additive that one kind according to claim 4 can introduce rubber composition, which is characterized in that the metal M
For calcium, iron, magnesium, titanium, aluminium or vanadium.
6. the preparation method of the additive a method as claimed in any one of claims 1 to 5 for introducing rubber composition, which is characterized in that packet
Include following steps:
(1) double carboxylic bronsted lowry acids and bases bronsted lowries are taken, or the salt of double carboxylic acids is directly taken to be placed in polar solvent, heats, until solution is fully transparent, obtains
To double carboxylic acid salt solution A；
(2) band alcoholic extract hydroxyl group aliphatic carboxylic acid and alkali are taken, or the salt with alcoholic extract hydroxyl group aliphatic carboxylic acid is directly taken to be placed in polar solvent,
Heating obtains band alcoholic extract hydroxyl group aliphatic carboxylate solution B until solution is fully transparent；
(3) under agitation, double carboxylic acid salt solution A, band alcoholic extract hydroxyl group aliphatic carboxylate solution B and configured metal are mixed
M salting liquid, reaction obtain solid product, filter, washing, dry to get arriving purpose product rubber additive；
The structural formula of double carboxylic acids are as follows: HOOC-R1-(AxBy)m-R2-COOH；
The structural formula with alcoholic extract hydroxyl group aliphatic carboxylic acid are as follows: (OH)a-R3- COOH or (OH)b-R4-COOH。
7. the preparation method of the additive according to claim 6 for introducing rubber composition, which is characterized in that double carboxylic acids
Double carboxylate products are to meet structural formula HOOC-R in salting liquid A1-(AxBy)m-R2The salt of one or more double carboxylic acids of-COOH
Product.
8. the preparation method of the additive according to claim 6 for introducing rubber composition, which is characterized in that described
Band alcoholic extract hydroxyl group aliphatic carboxylic acid is selected from jalapinolic acid, 16- hydroxyl Heptadecanoic acide, 12- hydroxyoctadecanoic acid, 6- hydroxyl
Nonadecylic acid, 11- hydroxyeicosanoic acid, 2- hydroxyl carboceric acid, 9,18- dihydroxy octadecanoid acid, 11,18- dihydroxy ten
Eight alkanoic acids, 8,19- dihydroxy nonadecylic acid, 9,19- dihydroxy nonadecylic acid, 10- hydroxydecanoic acid, trans-10-hydroxyl-2- decene
One of acid or gluconic acid.
9. the additive a method as claimed in any one of claims 1 to 5 for introducing rubber composition prepare rubber for tire, sole rubber,
Application in yielding rubber, coating, adhesive or chemical product.
10. the application of the additive according to claim 9 for introducing rubber composition, which is characterized in that the rubber
When glue additive is prepared for rubber for tire, sole rubber or yielding rubber, corresponding applicable rubber mass is thermoplastic elastic
Body or foaming elastomer；
When the rubber additive is used for coating preparation, corresponding applicable coating be acrylic compounds, polyurethanes, polyethers or
Epoxy resin coating；
When the rubber additive is prepared for adhesive, the base-material of corresponding applicable adhesive is natural material, synthesis is high
Molecular material and inorganic material；
When the rubber additive is prepared for chemical product, corresponding applicable chemical product is cosmetics, fragrance, soap or tooth
Cream.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418966A (en) * | 2015-12-21 | 2016-03-23 | 同济大学 | Rubber additive and preparation and application thereof |
| CN106831842A (en) * | 2016-12-29 | 2017-06-13 | 同济大学 | A kind of rubber additive and its preparation and application |
| CN106866444A (en) * | 2016-12-29 | 2017-06-20 | 同济大学 | A kind of rubber additive and its preparation and application |
-
2017
- 2017-12-15 CN CN201711346769.9A patent/CN108034077B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418966A (en) * | 2015-12-21 | 2016-03-23 | 同济大学 | Rubber additive and preparation and application thereof |
| CN106831842A (en) * | 2016-12-29 | 2017-06-13 | 同济大学 | A kind of rubber additive and its preparation and application |
| CN106866444A (en) * | 2016-12-29 | 2017-06-20 | 同济大学 | A kind of rubber additive and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| Modification of rubber with reactive filler. II. Modification of NBR with aluminum carboxylates having amino or hydroxyl groups;Yamada, Eisuke等;《Nippon Gomu Kyokaishi》;19831231;614页右栏3.1部分，table 3 * |
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