CN108218905A - A kind of amino-compound class rubber additive and its preparation and application - Google Patents
A kind of amino-compound class rubber additive and its preparation and application Download PDFInfo
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- CN108218905A CN108218905A CN201711347964.3A CN201711347964A CN108218905A CN 108218905 A CN108218905 A CN 108218905A CN 201711347964 A CN201711347964 A CN 201711347964A CN 108218905 A CN108218905 A CN 108218905A
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- amino
- acid
- acids
- rubber
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical class CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical class CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002545 isoxazoles Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000003831 tetrazolyl group Chemical group 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical class CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
- JJMDCOVWQOJGCB-UHFFFAOYSA-N 5-aminopentanoic acid Chemical class [NH3+]CCCCC([O-])=O JJMDCOVWQOJGCB-UHFFFAOYSA-N 0.000 description 1
- QCJTVQRPYDJCKS-UHFFFAOYSA-N C=[O]N=C1CC1 Chemical compound C=[O]N=C1CC1 QCJTVQRPYDJCKS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZXRRHFSTAFVGOC-UHFFFAOYSA-N [AlH3].[K] Chemical compound [AlH3].[K] ZXRRHFSTAFVGOC-UHFFFAOYSA-N 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- VCSZKSHWUBFOOE-UHFFFAOYSA-N dioxidanium;sulfate Chemical class O.O.OS(O)(=O)=O VCSZKSHWUBFOOE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000028755 loss of height Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/53—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings
-
- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of amino-compound class rubber additives and its preparation and application, chemical structural formula to be：, wherein, n is the oxidation state of metallic element M, n=2,3 or 4；A be oxygen, sulphur, carbon, nitrogen, phosphorus or silicon in one kind, 0≤x≤10；B be oxygen, sulphur, carbon, nitrogen, phosphorus or silicon in one kind, 0≤y≤10；(AxBy)mRepresent that atom is connected with chemical bond, x during y differences with taking 0；0≤m≤10；z≤50)；R1And R2Aliphatic chain, alicyclic or aromatic compound for carbon atom number 0 to 50；R3、R4、R6、R8For the saturated or unsaturated aliphatic chain or alicyclic of carbon atom number 0 to 50, R5With R7For aromatic cycle compound；A and b is positive integer.Additive prepared by the present invention can be applied to rubber, improve the hardness of rubber, wet-sliding resistant performance, dynamic mechanical and tensile property etc., rubber composition of the part containing additive all has the shore hardness improved, elongation at break, wet-sliding resistant performance and the dynamic modulus of elasticity.
Description
Technical field
The present invention relates to amino-compound class rubber additive fields, add more particularly, to a kind of amino-compound class rubber
Add agent and its preparation and application.
Background technology
Modulus of the raising for tread base composition and the sizing material of bead wire rubber cover is wished in tire industry.In order to
Improve the modulus of above-mentioned sizing material, it is common practice to as adding in a large amount of reinforced filling in these sizing materials, such as carbon black and titanium dioxide
Silicon or the state of cure (vulcanization) for improving these sizing materials.However, the effect that both technologies generate is unsatisfactory.For example, to rubber group
A large amount of charcoal clandestine meeting, which is added in, in conjunction object generally results in the hysteresis loss of height, therefore can be caused using this kind of sizing material in tire
Excessive accumulated heat and tear resistance are deteriorated.In another example a large amount of sulphur is added in into rubber composition generally results in formula
Anti-aging property be deteriorated, in addition, only usually improving state of cure (vulcanization) realizes that high-modulus is very unpractical.Based on upper
Reason is stated, develops a kind of tire amino-compound class rubber additive, glue can be improved after being added on a small quantity into rubber composition
Material modulus is unlikely to lead to being decreased obviously for other performances of sizing material again, is of great significance in tire industry.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of amino-compound classes
Rubber additive and its preparation and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of amino-compound class rubber additive, chemical structural formula are：
Wherein, n is the oxidation state of metallic element M, n=2,3 or 4；A is one kind in following atom：Oxygen, sulphur, carbon, nitrogen,
Phosphorus, silicon, 0≤x≤10；B is one kind in following atom：Oxygen, sulphur, carbon, nitrogen, phosphorus, silicon, 0≤y≤10；X during y differences with taking 0；
(AxBy)mRepresent 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、R4、R6、R8For the saturated or unsaturated aliphatic chain or alicyclic of carbon atom number 0 to 50, R5With R7
Aromatic cycle compound for carbon atom number 0 to 50；A and b is positive integer.
Represent amino (- NH2) R can be connected on3, R5Or R6On, and R3、R5、R6Altogether
It is connected at least one amino；
Represent amino (- NH2) R can be connected on4, R7Or R8On, and R4、R7、R8It is upper common
Meter connects at least one amino.
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；Ring is formed 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- triazoles, 1,2,4- triazoles, tetrazolium, oxazole, isoxazoles, thiazole, benzimidazole, benzotriazole,
Benzoxazole, benzothiazole, 2-methylimidazole, 3- picolines or 3- methylpyrazoles.
Preferably, the one kind of the metal M in following metallic element：
The metal of the metal of I B to VIII B races or II A to VI A races in the periodic table of elements；It is furthermore preferred that the metal M choosings
One kind from calcium, iron, magnesium, titanium, aluminium or vanadium；Even more preferably, the one kind of the metal M in calcium, magnesium and aluminium.
Preferably, as-R5When group is aromatic cycle compound ,-R3Group ,-R6Group with-R5Benzene in group
Ring connects；As-R7When group is aromatic cycle compound ,-R4Group ,-R8Group with-R7Phenyl ring connection in group.Even
The mode of connecing is preferably meta or para position connection.It is furthermore preferred that for contraposition connection.
Preferably, R3、R4、R6、R8On amino be primary amino group, secondary amino group and tertiary amino；It is furthermore preferred that R3、R4、R6、R8On
Amino be primary amino group and secondary amino group；It is furthermore preferred that R3、R4、R6、R8On amino be primary amino group.
A kind of preparation method of amino-compound class rubber additive, includes 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) it takes amino bronsted lowry acids and bases bronsted lowry or the salt of amino acid is directly taken to be placed in polar solvent, heat, until solution is completely saturating
It is bright, obtain amino acid salt solution B；
(3) under agitation, double carboxylic acid salt solution A, amino acid salt solution B and metal M salting liquids are mixed, is obtained by the reaction
Solid product filters, washing, dry to get to purpose product amino-compound class rubber additive；
The structural formula of double carboxylic acids is：HOOC-R1-(AxBy)m-R2-COOH；
The structural formula of the amino acid is：
I.e. represent amino acid structural formula be：(NH2)a-R6-R5-R3- COOH or (NH2)b-R8-R7-R4-COOH；It is in another example described
The structural formula of amino acid is：R6-R5(-(NH2)a)-R3- COOH or R8-R7(-(NH2)b)-R4-COOH。
Preferably, double carboxylates in double carboxylic acid salt solution A is meet structural formula HOOC-R1-(AxBy)m-R2- COOH's is double
It is one or more compound in the salt product of carboxylic acid；
Amino-acid salt in amino acid solution B is the salt product of one or more amino acid for meeting structural formula.
Preferably, the solution A, the order by merging of solution B and metallic element M salting liquids can be specially：Solution A is taken,
Under stirring condition, metal M salting liquids are poured into, obtain solution C, under agitation, solution B poured into solution C, will be obtained by the reaction
Solid product filters, washing, dry to get to purpose product additive.It is of course also possible to foregoing description is not limited to, with arbitrary
Sequence mixes, as long as final solid product can be obtained.
Preferably, the metal M salt can be anhydrous calcium chloride, Potassium aluminum sulfate dodecahydrate, aluminum sulfate, alchlor,
It is a kind of in anhydrous magnesium chloride, magnesium sulfate, ferric trichloride, titanium tetrachloride, titanium sulfate, 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,
In one kind；
The polar solvent be selected from water, tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide (DMSO), 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) is as a preferred embodiment of the above solution,：HOOC-R1-(AxBy)m-R2-
The preferred nitrogen of COOH, A and B, oxygen, sulphur；Preferred A and B is sulphur；
The one kind of amino acid in the organic compound simultaneously containing amino and carboxyl described in step (2), specifically
It may be selected from glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, tyrosine, silk ammonia
Acid, cysteine, methionine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, group
Propylhomoserin, 4-aminobenzoic acid, 5- aminovaleric acids, 5- amino -3 methylvaleric acid, 5- amino -4- methylvaleric acids, 3- aminocaproic acids,
5- aminocaproic acids, 6-aminocaprolc acid, 6- amino -2- propyl caproic acid, 2- aminoheptylic acids, 3- aminoheptylic acids, 6- aminoheptylic acids, 7- ammonia
Base enanthic acid, DL-2- aminocaprylic acids, 3- aminocaprylic acids, 8- aminocaprylic acids, 9 aminononanoic acid, 10- aminocapric acids, 11- amino 11
One kind in alkanoic acid, 12 amino dodecanoic acid.
As the preferred of above-mentioned amino-compound preparation method,
The double carboxylic acids and the molar ratio of alkali added in step (1) are (1~2)：2, alkali in polar solvent a concentration of 0.2
~0.4mol/L, the process conditions for heating reaction are：It is heated to 90 DEG C and is vigorously stirred 1h；；
The amino acid added in step (2) is single substance, and the molar ratio with alkali is (1~2)：2 or step (2) in
Directly add a kind of salt of amino acid, a concentration of 0.2~0.4mol/L of the alkali in polar solvent heats the process conditions of reaction
For：It is heated to 90 DEG C and is vigorously stirred 1h；；
In step (3)：For solution A, solution B and metal M salting liquids, preferred order by merging is that solution A pours into metal
M salting liquids obtain solution C, and solution B pours into A, a concentration of 0.30~0.50mol/L of metal M salting liquids again, drying after washing
Process conditions are：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 threes is (0.8~1.2):
(1.6~2.4):2, the speed that solution A pours into metal M salting liquids pours into the 1% of total solution A volume to be per second, and solution B is fallen
The speed for entering C pours into the 1% of total solution B volume to be per second.
A kind of amino-compound class rubber additive is preparing rubber for tire, sole rubber, yielding rubber, coating, gluing
Application in agent or chemical product.
When the amino-compound class rubber additive is prepared for rubber for tire as a preferred embodiment of the above solution, every 100
1~200 part of metallic soap (i.e. amino-compound class rubber additive) is added in the rubber mass of parts by weight, rubber
Other additives use the type and additive amount of the additive in traditional rubber.
It is right when the amino-compound class rubber additive is prepared for rubber for tire, sole rubber or yielding rubber
The rubber mass that should be applicable in is thermoplastic elastomer (TPE) or foaming elastomer, the specially butadiene-styrene rubber of thermoplasticity or foaming, butyronitrile
Rubber, natural rubber, organic silicon rubber, polyurethane rubber or isopropyl rubber etc.；
When the amino-compound class rubber additive is used for coating preparation, corresponding applicable coating is acrylic compounds,
Polyurethanes, polyethers or epoxy resin coating etc.；
When the amino-compound class rubber additive is prepared for adhesive, the base-material of corresponding applicable adhesive is
Natural material, synthesis high molecular material and inorganic material；
When the amino-compound class rubber additive is prepared for chemical product, corresponding applicable chemical product is makeup
Product, 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、R4、R6、R8Fat chain structure in group can be tangled with rubber molecule to react, R3-R8The amino of upper connection can be affine
The groups containing oxygen atom such as the hydroxyl on the common reinforced filling of rubber (such as carbon black, white carbon) surface, so as to reduce rubber
The generation of the three-dimensional netted mechanism of filler, is conducive to filler and disperses in rubber mass in glue；On the other hand, it is produced by the present invention to add
When adding the agent to be used to prepare rubber, in the additive-(AxBy)mAtom in group is connected with chemical bond, in the vulcanization of rubber
In the process, key fracture (bond cleavage) can occur under curing temperature and generate free radicals, these freedom for above-mentioned chemical bond
Base can be chemically reacted with the double bond in rubber mass, and the additive is helped to be connected on rubber mass strand；
Under the effect of above-mentioned both sides, amino-compound produced by the present invention be applied to rubber system for when, improve a variety of property of rubber
Energy.
Compared with prior art, amino-compound class rubber additive preparation process of the present invention is simple, and each component raw material is easy
, it is suitable for industrialized production；Additive for rubber system for when, solubility in rubber mass is high.From specific implementation
Exemplary embodiment in mode is it is found that the additive of the present invention can improve rubber in the rubber compoundings such as diene rubber
Shore hardness, elongation at break, wet-sliding resistant performance and the dynamic modulus of elasticity.
Specific embodiment
A kind of amino-compound class rubber additive, chemical structural formula are：
Wherein, n is the oxidation state of metallic element M, n=2,3 or 4；A is one kind in following atom：Oxygen, sulphur, carbon, nitrogen,
Phosphorus, silicon, 0≤x≤10；B is one kind in following atom：Oxygen, sulphur, carbon, nitrogen, phosphorus, silicon, 0≤y≤10；X during y differences with taking 0；
(AxBy)mRepresent 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、R4、R6、R8For the saturated or unsaturated aliphatic chain or alicyclic of carbon atom number 0 to 50, R5With R7
Aromatic cycle compound for carbon atom number 0 to 50；A and b is positive integer.
Represent amino (- NH2) R can be connected on3, R5Or R6On, and R3、R5、R6Altogether
It is connected at least one amino；
Represent amino (- NH2) R can be connected on4, R7Or R8On, and R4、R7、R8It is upper common
Meter connects at least one amino.
As the preferred embodiment of said program, 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 ring is formed 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- triazoles, 1,2,4- triazoles, tetrazolium, oxazole, isoxazoles, thiazole, benzo miaow
Azoles, benzotriazole, benzoxazole, benzothiazole, 2-methylimidazole, 3- picolines or 3- methylpyrazoles.
As the preferred embodiment of said program, the one kind of the metal M in following metallic element：
The metal of the metal of I B to VIII B races or II A to VI A races in the periodic table of elements；It is furthermore preferred that the metal M choosings
One kind from calcium, iron, magnesium, titanium, aluminium or vanadium；Even more preferably, the one kind of the metal M in calcium, magnesium and aluminium.
As the preferred embodiment of said program, as-R5When group is aromatic cycle compound ,-R3Group ,-R6-
Group with-R5Phenyl ring connection in group；As-R7When group is aromatic cycle compound ,-R4Group ,-R8Group with-
R7Phenyl ring connection in group.Connection mode is preferably meta or para position connection.It is furthermore preferred that for contraposition connection.
As the preferred embodiment of said program, R3、R4、R6、R8On amino be primary amino group, secondary amino group and tertiary ammonia
Base；It is furthermore preferred that R3、R4、R6、R8On amino be primary amino group and secondary amino group；It is furthermore preferred that R3、R4、R6、R8On amino be primary
Amino.
A kind of preparation method of amino-compound class rubber additive, includes 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) it takes amino bronsted lowry acids and bases bronsted lowry or the salt of amino acid is directly taken to be placed in polar solvent, heat, until solution is completely saturating
It is bright, obtain amino acid salt solution B；
(3) under agitation, double carboxylic acid salt solution A, amino acid salt solution B and metal M salting liquids are mixed, is obtained by the reaction
Solid product filters, washing, dry to get to purpose product amino-compound class rubber additive；
The structural formula of double carboxylic acids is：HOOC-R1-(AxBy)m-R2-COOH；
The structural formula of the amino acid is：
I.e. represent amino acid structural formula be：(NH2)a-R6-R5-R3- COOH or (NH2)b-R8-R7-R4-COOH；It is in another example described
The structural formula of amino acid is：R6-R5(-(NH2)a)-R3- COOH or R8-R7(-(NH2)b)-R4-COOH。
As the preferred embodiment of said program, double carboxylates in double carboxylic acid salt solution A is meet structural formula
HOOC-R1-(AxBy)m-R2It is one or more compound in the salt product of double carboxylic acids of-COOH；
Amino-acid salt in amino acid solution B is the salt product of one or more amino acid for meeting structural formula.
As the preferred embodiment of said program, the solution A, the mixing of solution B and metallic element M salting liquids is suitable
Sequence can be specially：Solution A is taken, under agitation, metal M salting liquids is poured into, obtains solution C, under agitation, to solution
C pours into solution B, and solid product will be obtained by the reaction, and filters, washing, dry to get to purpose product additive.It is of course also possible to
Foregoing description is not limited to, is mixed with random order, as long as final solid product can be obtained.
As the preferred embodiment of said program, the metal M salt can be anhydrous calcium chloride, ten sulfate dihydrates
One in aluminium potassium, aluminum sulfate, alchlor, anhydrous magnesium chloride, magnesium sulfate, ferric trichloride, titanium tetrachloride, titanium sulfate, vanadium trichloride
Kind.
As the preferred embodiment of said program, the alkali is selected from sodium hydroxide, potassium hydroxide, potassium carbonate, carbon
One kind in sour sodium or ammonium hydroxide；
The polar solvent be selected from water, tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide (DMSO), 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) is as a preferred embodiment of the above solution,：HOOC-R1-(AxBy)m-R2-
The preferred nitrogen of COOH, A and B, oxygen, sulphur；Preferred A and B is sulphur；
The one kind of amino acid in the organic compound simultaneously containing amino and carboxyl described in step (2), specifically
It may be selected from glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, tyrosine, silk ammonia
Acid, cysteine, methionine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, group
Propylhomoserin, 4-aminobenzoic acid, 5- aminovaleric acids, 5- amino -3 methylvaleric acid, 5- amino -4- methylvaleric acids, 3- aminocaproic acids,
5- aminocaproic acids, 6-aminocaprolc acid, 6- amino -2- propyl caproic acid, 2- aminoheptylic acids, 3- aminoheptylic acids, 6- aminoheptylic acids, 7- ammonia
Base enanthic acid, DL-2- aminocaprylic acids, 3- aminocaprylic acids, 8- aminocaprylic acids, 9 aminononanoic acid, 10- aminocapric acids, 11- amino 11
One kind in alkanoic acid, 12 amino dodecanoic acid.
As the preferred embodiment of above-mentioned amino-compound preparation method,
The double carboxylic acids and the molar ratio of alkali added in step (1) are (1~2)：2, alkali in polar solvent a concentration of 0.2
~0.4mol/L, the process conditions for heating reaction are：It is heated to 90 DEG C and is vigorously stirred 1h；；
The amino acid added in step (2) is single substance, and the molar ratio with alkali is (1~2)：2 or step (2) in
Directly add a kind of salt of amino acid, a concentration of 0.2~0.4mol/L of the alkali in polar solvent heats the process conditions of reaction
For：It is heated to 90 DEG C and is vigorously stirred 1h；；
In step (3)：For solution A, solution B and metal M salting liquids, preferred order by merging is that solution A pours into metal
M salting liquids obtain solution C, and solution B pours into A, a concentration of 0.30~0.50mol/L of metal M salting liquids again, drying after washing
Process conditions are：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 threes is (0.8~1.2):
(1.6~2.4):2, the speed that solution A pours into metal M salting liquids pours into the 1% of total solution A volume to be per second, and solution B is fallen
The speed for entering C pours into the 1% of total solution B volume to be per second.
A kind of amino-compound class rubber additive is preparing rubber for tire, sole rubber, yielding rubber, coating, gluing
Application in agent or chemical product.
As the preferred embodiment of said program, the amino-compound class rubber additive is prepared for rubber for tire
When, 1~200 part of metallic soap (i.e. amino-compound class rubber additive), rubber are added in the rubber mass of every 100 parts by weight
Other additives of glue product use the type and additive amount of the additive in traditional rubber.
It is right when the amino-compound class rubber additive is prepared for rubber for tire, sole rubber or yielding rubber
The rubber mass that should be applicable in is thermoplastic elastomer (TPE) or foaming elastomer, the specially butadiene-styrene rubber of thermoplasticity or foaming, butyronitrile
Rubber, natural rubber, organic silicon rubber, polyurethane rubber or isopropyl rubber etc.；
When the amino-compound class rubber additive is used for coating preparation, corresponding applicable coating is acrylic compounds,
Polyurethanes, polyethers or epoxy resin coating etc.；
When the amino-compound class rubber additive is prepared for adhesive, the base-material of corresponding applicable adhesive is
Natural material, synthesis high molecular material and inorganic material；
When the amino-compound class rubber additive is prepared for chemical product, corresponding applicable chemical product is makeup
Product, fragrance, soap or toothpaste etc..
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of amino-compound, chemical structural formula are：
The preparation method of above-mentioned additive, includes the following steps：
(1) 1L distilled water and 16g sodium hydrate solids (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 acids (purity >=99.0% (GC) (T), purchase are added in
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 solids (purity >=97%, purchased from me are added in the beaker of a 2L
Fourth).After sodium hydroxide is completely dissolved, 54.85g 4-aminobenzoic acid (purity >=98%, purchased from Aladdin) is added in.It will be upper
It states mixture to be heated to 90 DEG C and be vigorously stirred 1 hour, until solution is fully transparent.(solution D)
(3) take the beaker of a 4L again, add in thereto 1L distilled water and 189.76g Potassium aluminum sulfate dodecahydrates (purity >=
99%, 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) and then in the case where being vigorously stirred solution B, solution A is slowly poured into solution B with the speed of 10mL/s,
Obtain solution C.
(5) and then in the case where being vigorously stirred solution C, solution D is slowly poured into solution C with the speed of 10mL/s,
Obtain white solid product.The white solid product distillation washing 5 times of gained will be filtered, then put it into vacuum drying oven 90
DEG C vacuum drying 12 hours after by oven temperature rise to 110 DEG C continue vacuum drying 12 hours.Final product for white powder (i.e.
For purpose product).
Embodiment 2
A kind of amino-compound, chemical structural formula are：
The preparation method of above-mentioned additive, includes the following steps：
(1) 1L distilled water and 16g sodium hydrate solids (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 acids (purity >=99.0% (GC) (T), purchase are added in
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 97%, is purchased from for addition 1L distilled water and 80.52g 11- amino undecanoic acids in the beaker of a 2L
Aladdin).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, add in thereto 1L distilled water and 189.76g Potassium aluminum sulfate dodecahydrates (purity >=
99%, 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) and then in the case where being vigorously stirred solution B, solution A is slowly poured into solution B with the speed of 10mL/s,
Obtain solution C.
(5) and then in the case where being vigorously stirred solution C, solution D is slowly poured into solution C with the speed of 10mL/s,
Obtain white solid product.The white solid product distillation washing 5 times of gained will be filtered, then put it into vacuum drying oven 90
DEG C vacuum drying 12 hours after by oven temperature rise to 110 DEG C continue vacuum drying 12 hours.Final product for white powder (i.e.
For purpose product).
Embodiment 3-5
The amination obtained by embodiment 1-2 is separately added into the rubber composition using white carbon as main reinforced filling
Object is closed, wherein, Rubber mix formulations are as shown in table 1.Blank control Rubber mix formulations as shown in embodiment 3 in table 1,
1 the resulting product of embodiment is added in the rubber composition of embodiment 4, reality is added in the rubber composition of embodiment 5
Apply 2 the resulting product of example.The specific mixing step of filler, auxiliary agent, vulcanizing agent etc. is listed in Table 2 in embodiment 3-5.Embodiment
The product of 1-2 adds in simultaneously with reinforced filling.Rubber composition after mixing slice on a mill, then uses vulcanizing press
Cured, solidification temperature is 150 DEG C, and hardening time is for 30 minutes to get to rubber sample.
The formula table of 1 embodiment 3-5 of table
2 compounding conditions table of table
Rubber sample made from embodiment 3-5 is carried out solidified sample hardness, extension test, dynamic mechanical test with
And wet and slippery test, detection data are listed in Table 3 below.It can be seen that from the data of table 3：White carbon is mixed for the rubber of main reinforced filling
It closes in object, blank sample is compared with the rubber sample for being added to embodiment 1, embodiment 2, adds amino-compound described in 10Phr
Sample later all has the shore hardness improved, elongation at break, with the anti-slippery of mono-pendulum type friction coefficient tester characterization
Storage modulus at performance and 60 DEG C；Sample after amino-compound described in part addition 10Phr has reduction at 60 DEG C
Fissipation factor.
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 during test.Test sample is ring
Shape, ring internal diameter 14.0mm, ring outer diameter 16.0mm, height 3.00mm.
Anton Paar EC302 rheometers are 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 is：60 DEG C, under 0.5 hertz of frequency strain from
0.001% to 15% strain sweep.
Embodiment 6
A kind of preparation method of amino-compound, includes the following steps：
(1) added in the beaker of a 2L 1L distilled water and 0.4mol sodium hydrate solids (purity >=97%, purchased from Ah
Latin).After sodium hydroxide is completely dissolved, addition 0.2mol 3,3'- dithiodipropionic acids (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) added in the beaker of a 2L 1L distilled water and 0.4mol sodium hydrate solids (purity >=97%, purchased from Ah
Latin).After sodium hydroxide is completely dissolved, addition 0.4mol 12 amino dodecanoic acids (>98.0% (T), purchased from TCI).It will
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, add in thereto 1L distilled water and 0.4mol Potassium aluminum sulfate dodecahydrates (purity >=
99%, 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) and then in the case where being vigorously stirred solution B, solution A is slowly poured into solution B with the speed of 10mL/s,
Obtain solution C.
(5) and then in the case where being vigorously stirred solution C, solution D is slowly poured into solution C with the speed of 10mL/s,
Obtain white solid product.The white solid product distillation washing 5 times of gained will be filtered, then put it into vacuum drying oven 90
DEG C vacuum drying 12 hours after by oven temperature rise to 110 DEG C continue vacuum drying 12 hours.Final product for white powder (i.e.
For purpose product).
Embodiment 7
In addition to the addition of sodium hydroxide in step (1) is changed to 0.30mol, the addition of 3,3'- dithiodipropionic acids changes
For 0.15mol；The addition of sodium hydroxide is changed to 0.30mol in step (2), and the addition of 12 amino dodecanoic acid is changed to
0.30mol；The addition 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 addition of sodium hydroxide in step (1) is changed to 0.2mol, the addition of 3,3'- dithiodipropionic acids is changed to
0.1mol；The addition of sodium hydroxide is changed to 0.2mol in step (2), and the addition of 12 amino dodecanoic acid is changed to 0.1mol；
The addition of Potassium aluminum sulfate dodecahydrate is changed to outside 0.20mol in step (3), remaining is in the same manner as in Example 6.
Embodiment 9-11
The amination obtained by embodiment 6-8 is separately added into the rubber composition using white carbon as main reinforced filling
Object is closed, is obtained such as the Rubber mix formulations of embodiment 9-11, can specifically be shown in Table 4 (9 corresponding embodiment 6 of embodiment, successively
Analogize).
The formula table of 4 embodiment 9-11 of table
The mixing such as 2 compounding conditions of table is carried out to get to rubber sample according to above-mentioned formula.
Embodiment 12-47
Compared with Example 6, the overwhelming majority it is all identical, in addition in the present embodiment by 12 amino dodecanoic acid in step (2)
Glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, the color ammonia of equimolar amounts are replaced with respectively
Acid, serine, cysteine, methionine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, relies tyrosine
Propylhomoserin, arginine, histidine, 5- aminovaleric acids, 5- amino -3 methylvaleric acid, 5- amino -4- methylvaleric acids, 3- aminocaproic acids,
5- aminocaproic acids, 6-aminocaprolc acid, 6- amino -2- propyl caproic acid, 2- aminoheptylic acids, 3- aminoheptylic acids, 6- aminoheptylic acids, 7- ammonia
Base enanthic acid, DL-2- aminocaprylic acids, 3- aminocaprylic acids, 8- aminocaprylic acids, 9 aminononanoic acid or 10- aminocapric acids.
Embodiment 48-51
Compared with Example 6, the overwhelming majority is all identical, in addition to accordingly replacing with sodium hydroxide respectively in the present embodiment
Potassium hydroxide, potassium carbonate, sodium carbonate or the ammonium hydroxide of mole.
Embodiment 52-62
Compared with Example 6, the overwhelming majority is all identical, in addition to replacing with polar solvent distilled water respectively in the present embodiment
Tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide (DMSO), 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 can easily make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to above-described embodiment, abilities
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 the present invention's
Within protection domain.
Claims (10)
1. a kind of amino-compound class rubber additive, which is characterized in that its chemical structural formula is：
Wherein, n represents the oxidation state of metal M, value 2,3 or 4；
A be oxygen, sulphur, carbon, nitrogen, phosphorus or silicon in one kind, 0≤x≤10；
B be oxygen, sulphur, carbon, nitrogen, phosphorus or silicon in one kind, 0≤y≤10；
(AxBy)mRepresent that atom is connected with chemical bond, and x during y differences with taking 0；
0≤m≤10, z≤50, a and b are positive integer；
R1And R2Aliphatic chain, alicyclic or aromatic compound for carbon atom number 0 to 50；R3、R4、R6、R8For carbon atom number 0 to 50
Aliphatic chain or alicyclic, R5With R7Aromatic compound for carbon atom number 0 to 50.
A kind of 2. amino-compound class rubber additive according to claim 1, which is characterized in that R3、R5And R6Connect altogether
It is connected at least one amino；
R4、R7、R8It is upper to connect at least one amino altogether；
The aromatic compound is benzene, phenyl ring polymer or heterocyclic compound.
A kind of 3. amino-compound class rubber additive according to claim 1, which is characterized in that-R3Group ,-R6Base
Group with-R5Aromatic rings or fatty chain link in group；-R4Group ,-R8Group with-R7Aromatic rings in group or
Fatty chain link.
A kind of 4. amino-compound class rubber additive according to claim 1, which is characterized in that the metal M choosings
One kind from following metallic element：
The metal of the metal of I B to VIII B races or II A to VI A races in the periodic table of elements.
5. a kind of amino-compound class rubber additive according to claim 4, which is characterized in that the metal M is
Calcium, iron, magnesium, titanium, aluminium or vanadium.
6. the preparation method of the amino-compound class rubber additive as described in claim 1-5 is any, which is characterized in that including
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) it takes amino bronsted lowry acids and bases bronsted lowry or the salt of amino acid is directly taken to be placed in polar solvent, heat, until solution is fully transparent, obtain
To amino acid salt solution B；
(3) under agitation, double carboxylic acid salt solution A, amino acid salt solution B and metal M salting liquids are mixed, solid is obtained by the reaction
Product filters, washing, dry to get to purpose product amino-compound class rubber additive；
The structural formula of double carboxylic acids is：HOOC-R1-(AxBy)m-R2-COOH；
The structural formula of the amino acid is：
A kind of 7. preparation method of amino-compound class rubber additive according to claim 6, which is characterized in that double carboxylics
Double carboxylates in acid salt solution A is meet structural formula HOOC-R1-(AxBy)m-R2One in the salt product of double carboxylic acids of-COOH
Kind or it is a variety of compound；
Amino-acid salt in amino acid solution B is the salt product of one or more amino acid for meeting structural formula.
A kind of 8. preparation method of amino-compound class rubber additive according to claim 6, which is characterized in that step
(2) amino acid described in is selected from glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, color
Propylhomoserin, tyrosine, serine, cysteine, methionine, asparagine, glutamine, threonine, aspartic acid, glutamic acid,
Lysine, arginine, histidine, 4-aminobenzoic acid, 5- aminovaleric acids, 5- amino -3 methylvaleric acid, 5- amino -4- methyl
Valeric acid, 3- aminocaproic acids, 5- aminocaproic acids, 6-aminocaprolc acid, 6- amino -2- propyl caproic acid, 2- aminoheptylic acids, 3- amino heptan
Acid, 6- aminoheptylic acids, 7- aminoheptylic acids, DL-2- aminocaprylic acids, 3- aminocaprylic acids, 8- aminocaprylic acids, 9 aminononanoic acid, 10- ammonia
One kind in base capric acid, 11- amino undecanoic acids or 12 amino dodecanoic acid.
9. the amino-compound class rubber additive as described in claim 1-5 is any is preparing rubber for tire, sole rubber, is subtracting
Shake the application in rubber, coating, adhesive or chemical product.
10. the application of amino-compound class rubber additive according to claim 8, which is characterized in that the amino
When compounds rubber additive is prepared for rubber for tire, sole rubber or yielding rubber, corresponding applicable rubber mass is
Thermoplastic elastomer (TPE) or foaming elastomer；
When the amino-compound class rubber additive is used for coating preparation, corresponding applicable coating is acrylic compounds, poly- ammonia
Esters, polyethers or epoxy resin coating；
When the amino-compound class rubber additive is prepared for adhesive, the base-material of corresponding applicable adhesive is natural
Material, synthesis high molecular material and inorganic material；
When the amino-compound class rubber additive is prepared for chemical product, corresponding applicable chemical product is cosmetics, perfume (or spice)
Material, soap or toothpaste.
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| CN111171376A (en) * | 2020-01-08 | 2020-05-19 | 株洲时代新材料科技股份有限公司 | Hindered phenol antioxidant and preparation method and application thereof |
| CN111171376B (en) * | 2020-01-08 | 2021-06-15 | 株洲时代新材料科技股份有限公司 | Hindered phenol antioxidant and preparation method and application thereof |
| CN113216039A (en) * | 2021-05-18 | 2021-08-06 | 河南章全机电设备有限公司 | Hydraulic lifting column |
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