CN105061808B - A kind of preparation method of rubber antioxidant - Google Patents
A kind of preparation method of rubber antioxidant Download PDFInfo
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- CN105061808B CN105061808B CN201510539169.9A CN201510539169A CN105061808B CN 105061808 B CN105061808 B CN 105061808B CN 201510539169 A CN201510539169 A CN 201510539169A CN 105061808 B CN105061808 B CN 105061808B
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Abstract
The invention discloses a kind of preparation method of rubber antioxidant, comprise the following steps：(1) age resistor dispersion liquid：P phenylenediamine type antioxidant is added in organic solvent, ultrasonic disperse is uniform under normal temperature, obtains age resistor dispersion liquid；(2) monomer graft reaction：Water and polymerization inhibitor are added in the age resistor dispersion liquid obtained under agitation to step (1), methacrylate-based monomer is added dropwise after stirring, reaction temperature is controlled at 60~70 DEG C；(3) it is aged：After methacrylate-based monomer drips, continue to stir more than 20min, then heat to 80~90 DEG C, the 13h of insulation reaction 11, be cooled to room temperature afterwards, product is obtained after extracting, washing, drying.The present invention is modified p phenylenediamine type antioxidant by GMA, various functions active site is introduced to reach the lifting of combination property, the aging action of p phenylenediamine type antioxidant can not only be ensured, make age resistor that graft crosslinking reaction occur on rubber molecular chain in sulfidation simultaneously, so as to reduce the generation of migration stain phenomenon, vulcanization promotion and reinforcement tool to rubber are greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of Novel rubber antioxidant, and in particular to a kind of methyl propenoic acid glycidyl
The preparation method of ester graft modification p phenylenediamine type antioxidant.
Background technology
Rubber is influenceed during storage and use by environmental factors such as oxygen, ozone, light, heat, it may occur that becomes
Color, bloom, it is tacky, be hardened, embrittlement, crackle etc.；Occur mechanical performance reduction, intensity and elongation of rubber etc. simultaneously significantly
Decline, phenomena such as gas permeability enhancing, dielectric properties weaken, these securities and service life all to rubber produce great
Influence.
At present, natural rubber (NR) is the maximum rubber of usage amount, has excellent mechanics and processing characteristics, and valency
Lattice are cheap, but it is because containing substantial amounts of unsaturated bond, it is easy to chemically react so that its ageing properties are not ideal enough.
In order to delay the ageing-resistant performance of unsaturated rubber, age resistor is often added in sizing material, it is anti-its object is to destroy oxidation chain type
Should, free radical is captured, the progress for terminating living chain to suppress or delaying aging reacts.Before 60 or seven ten years, amine basic body
The age resistor of system begins to use, especially p phenylenediamine type antioxidant, has good heat resistanceheat resistant oxygen and ozone resistance, is one
The rubber age resistor of kind function admirable.
In recent years, as the continuous development of rubber and high polymer material, the age resistor of simple function can not meet
Its demand.In order to solve the single anti-aging problem of rubber, people pass through the side such as compound, chemically react to amines antioxidants
A kind of multi-functional age resistor is prepared in method, while reaching good antiageing effect, also to the comprehensive of rubber
Influence can be generated.The method that age resistor is modified at present is more, such as Chinese patent CN1858035A, with 4-ADPA and contains
The aliphatic ketone for having two methyl is raw material, and new p-phenylenediamine rubber antioxidant FA0-7 has been prepared, and applied to rubber
Anti-aging.And for example, Chinese patent CN101165086A is prepared for spherical p-phenylenediamine rubber aging inhibitor N-1,3 dimethyl butyrates
Base-N'- diphenyl-para-phenylene diamines and N- isopropyl-N'- diphenyl-para-phenylene diamines, are advantageous to mixing of the rubber chemicals in compounding rubber
With it is scattered, and reach anti-aging effect in rubber.But these method of modifying exist one it is common the problem of, be exactly prepared for
A kind of p phenylenediamine type antioxidant for being applied to only single anti-aging effect in rubber, the vulcanization promotion property for elastomeric material
The raisings such as energy, mechanical property do not have an impact.Meanwhile when dosage reaches certain value, easily migrate to surface, cause
Pollution, influence the quality of rubber product.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of glycidyl methacrylate graft to be modified p-phenylenediamine
The method of class age resistor, ultrasound prepares age resistor dispersion liquid to the present invention in organic solvent first, is then added in dispersion liquid
GMA, and in the presence of catalyst and polymerization inhibitor, complete the modification of p phenylenediamine type antioxidant.
The present invention is achieved through the following technical solutions:
A kind of preparation method of rubber antioxidant, comprises the following steps:
(1) age resistor dispersion liquid：P phenylenediamine type antioxidant is added in organic solvent, ultrasonic disperse is equal under normal temperature
It is even, obtain age resistor dispersion liquid；The normal temperature refers to 25-30 DEG C；
(2) monomer graft reaction：Deionized water is added in the age resistor dispersion liquid obtained under agitation to step (1)
And polymerization inhibitor, methacrylate-based monomer is added dropwise after stirring, reaction temperature is controlled at 50~70 DEG C；
(3) it is aged：After methacrylate-based monomer drips, continue to stir more than 20min, then heat to 80~
90 DEG C, insulation reaction 11-13h, room temperature is cooled to afterwards, product is obtained after extracting, washing, drying.
Described p phenylenediamine type antioxidant and the mol ratio of methacrylate-based monomer are 1:2.05~2.15.
The p phenylenediamine type antioxidant is N- isopropyl-N'- diphenyl-para-phenylene diamines, N- cyclohexyl-N'- phenyl -1,4-
P-phenylenediamine, N, bis--iso-octyl of N'- p-phenylenediamine, N, N'- bis- (2- naphthyls) p-phenylenediamine, N, N'- DTPD di tolyl p phenylenediamines
Or one kind of N- (1,3- dimethylbutyls)-N'- diphenyl-para-phenylene diamines.The methacrylate-based monomer is methacrylic acid
Ethylene oxidic ester.
The dosage of the polymerization inhibitor is the 1% ~ 5% of p phenylenediamine type antioxidant quality, and the dosage of water is prevented for p-phenylenediamine class
The 10% ~ 20% of old agent quality.
The polymerization inhibitor be hydroquinones, hydroquinones monobutyl ether, the tert-butyl group lead benzenediol, 2- TBHQs or
One kind of 2,5 di tert butyl hydroquinone.
The organic solvent is acetone, toluene, ethyl acetate, dichloromethane, methanol, ethanol, acetonitrile or tetrahydrofuran
It is one or more kinds of.
It is the reaction mechanism that glycidyl methacrylate graft is modified p phenylenediamine type antioxidant below, with N- isopropyls
Exemplified by the graft modification of base-N '-diphenyl-para-phenylene diamine：
GMA has unstable cyclic structure, and chemical property is active, easily reacts.
Electron cloud in unshared electron pair and phenyl ring in p-phenylenediamine on nitrogen-atoms forms conjugated system, and reaction just occurs in nitrogen
On atom.Although GMA and p phenylenediamine type antioxidant are all nonpolar molecules, because polarity is organic
The presence of solvent, meanwhile, using water as catalyst, be advantageous to being smoothed out for addition reaction.Water is sweet with Glycidyl methacrylate
Grease can dissolve each other, and make N- isopropyls-N '-phenyl-Isosorbide-5-Nitrae-phenylenediamine be in alkaline solution, under alkaline state ,-NH in molecule
Steric hindrance is weaker, and therefore, the ring-opening reaction of oxygen bridge fracture is relatively easy to occur.
The present invention compared with prior art, has the following advantages that：
P phenylenediamine type antioxidant dispersion liquid and GMA are well mixed by the present invention first, are being urged
In the presence of agent and polymerization inhibitor, epoxy radicals in GMA can be in attack p phenylenediamine type antioxidant
Nitrogen-atoms, realize open loop be grafted.
The present invention is modified p phenylenediamine type antioxidant by GMA, introduces various functionsization activity
Point is to reach the lifting of combination property, and the methyl acrylic ester graft modification p-phenylenediamine class with epoxide group is anti-old
It agent, can not only ensure the aging action of p phenylenediamine type antioxidant, while by introducing unsaturated active site, age resistor is existed
Graft crosslinking reaction occurs in sulfidation on rubber molecular chain, so as to reduce the generation of migration stain phenomenon, and meanwhile it is right
Vulcanization promotion and the reinforcement tool of rubber are greatly improved, and are advantageous to further expand the potential application model of rubber age resistor
Enclose.
Brief description of the drawings
Fig. 1 is antioxidant 4010, the infrared spectrum collection of illustrative plates of antioxidant 4010NA.
Fig. 2 is the infrared spectrogram of GMA.
Fig. 3 is that the glycidyl methacrylate graft prepared by embodiment 1 ~ 3 is modified the infrared of antioxidant 4010NA
Spectrogram.
Fig. 4 is the infrared light of the glycidyl methacrylate graft modification antioxidant 4010 prepared by embodiment 4 ~ 5
Spectrogram.
This collection of illustrative plates is measured with " the Migna760 Fourier transformation infrared spectrometers that Nicolet companies of the U.S. produce ".
For GMA, 2900 ~ 3100cm-1Place's peak band belongs to-CH3、-CH2It is symmetrical and not right
Claim stretching vibration, 1720cm-1It is C=O stretching vibration absworption peak, 1638cm-1It is the stretching vibration absworption peak of C=C double bonds,
1435 and 1296cm-1It is C-H in-plane bending vibration absworption peaks, 908cm-1、844cm-1And 815cm-1It is then epoxy skeletal vibration spy
Levy absworption peak.The infrared spectrum collection of illustrative plates of antioxidant 4010 and antioxidant 4010NA is substantially coincident.3350cm-1Place nearby occurs
Stronger absworption peak, is the stretching vibration absworption peak that belongs to-NH, 2860 ~ 3050cm-1Place's absworption peak band is ownership
In-CH3、-CH2Symmetrical and asymmetric stretching vibration, and phenyl ring on C-H stretching vibration absworption peaks, 1598cm-1It is C-N
Stretching vibration absworption peak, 1497cm-1And 1515cm-1It is the vibration performance absworption peak of monosubstituted phenyl ring and disubstituted phenyl ring.And first
The antioxidant 4010 and antioxidant 4010NA of base glycidyl acrylate graft modification, in 3300 ~ 3650cm-1Place occurs
Obvious broad peak, it is vibration absorption peak caused by the-OH generated in epoxy ring-opening process of grafting, meanwhile,
908cm-1、844cm-1And 815cm-1The epoxy skeletal vibration characteristic absorption peak at place disappears substantially, illustrates open loop graft reaction
Success occurs.In addition, also occurs C=O stretching vibration absworption peak (1720cm in collection of illustrative plates-1) and C=C double bonds stretching vibration
Absworption peak (1638cm-1).Prevent always as can be seen that the present invention is successfully prepared into a kind of glycidyl methacrylate graft and is modified
Agent 4010 and antioxidant 4010NA.
Embodiment
Embodiment 1：
(1) age resistor dispersion liquid：4.93g (0.01mol) N- isopropyl-N'- diphenyl-para-phenylene diamines (4010NA) are added
Enter in 200ml acetone, the ultrasonic disperse 1h under normal temperature, obtain uniform age resistor dispersion liquid；
(2) monomer graft reaction：The age resistor dispersion liquid obtained in step (1) is transferred to three with condensing unit
In mouth bottle, and 0.5g deionized waters and 0.05g hydroquinones are added, keep continuing magnetic force stirring afterwards, 2.911g is slowly added dropwise
(0.0205mol) GMA, during dropwise addition, reaction temperature is controlled at 60~70 DEG C；
(3) it is aged：After GMA drips, reaction solution continues to stir 30min, then heats up
To 80~90 DEG C, insulation reaction 12h, room temperature, extracting, washing, drying to Glycidyl methacrylate are naturally cooled to afterwards
Glyceride graft modification p phenylenediamine type antioxidant.
Obtained glycidyl methacrylate graft is modified p phenylenediamine type antioxidant, with reference to right before and after graft modification
The change of phenylenediamine age resistor quality calculates grafting rate as 22.5%.
Embodiment 2：
(1) age resistor dispersion liquid：4.93g (0.01mol) N- isopropyl-N'- diphenyl-para-phenylene diamines (4010NA) are added
Enter in 200ml acetone, the ultrasonic disperse 1h under normal temperature, obtain uniform age resistor dispersion liquid；
(2) monomer graft reaction：The age resistor dispersion liquid obtained in step (1) is transferred to three with condensing unit
In mouth bottle, and 0.75g deionized waters and 0.15g hydroquinones are added, keep continuing magnetic force stirring afterwards, 2.982g is slowly added dropwise
(0.021mol) GMA, during dropwise addition, reaction temperature is controlled at 60~70 DEG C；
(3) it is aged：After methacrylate-based monomer drips, continue to stir 30min, then heat to 80~90
DEG C, insulation reaction 12h naturally cools to room temperature afterwards, and extracting, washing and drying connect to GMA
The modified p phenylenediamine type antioxidant of branch.
Obtained glycidyl methacrylate graft is modified p phenylenediamine type antioxidant, with reference to right before and after graft modification
The change of phenylenediamine age resistor quality calculates grafting rate as 28.2%.
Embodiment 3：
(1) age resistor dispersion liquid：4.93g (0.01mol) N- isopropyl-N'- diphenyl-para-phenylene diamines (4010NA) are added
Enter in 200ml acetone, the ultrasonic disperse 1h under normal temperature, obtain uniform age resistor dispersion liquid；
(2) monomer graft reaction：The age resistor dispersion liquid obtained in step (1) is transferred to three with condensing unit
In mouth bottle, and 1.0g deionized waters and 0.25g hydroquinones are added, keep continuing magnetic force stirring afterwards, 3.053g is slowly added dropwise
(0.0215mol) GMA, during dropwise addition, reaction temperature is controlled at 60~70 DEG C；
(3) it is aged：After methacrylate-based monomer drips, continue to stir 30min, then heat to 80~90
DEG C, insulation reaction 12h naturally cools to room temperature afterwards, and extracting, washing, drying connect to GMA
The modified p phenylenediamine type antioxidant of branch.
Obtained glycidyl methacrylate graft is modified p phenylenediamine type antioxidant, with reference to right before and after graft modification
The change of phenylenediamine age resistor quality calculates grafting rate as 23.6%.
Embodiment 4：
(1) age resistor dispersion liquid：2.66g (0.01mol) N cyclohexyl N' phenyl P phenylene diamine (4010) is added
In 200ml acetone, the ultrasonic disperse 1h under normal temperature, uniform age resistor dispersion liquid is obtained；
(2) monomer graft reaction：The age resistor dispersion liquid obtained in step (1) is transferred to three with condensing unit
In mouth bottle, and 0.3g deionized waters and 0.0266g hydroquinones are added, keep continuing magnetic force stirring afterwards, be slowly added dropwise
2.911g (0.0205mol) GMA, during dropwise addition, reaction temperature is controlled at 60~70 DEG C；
(3) it is aged：After methacrylate-based monomer drips, continue to stir 30min, then heat to 80~90
DEG C, insulation reaction 12h naturally cools to room temperature afterwards, and extracting, washing, drying connect to GMA
The modified p phenylenediamine type antioxidant of branch.
Obtained glycidyl methacrylate graft is modified p phenylenediamine type antioxidant, with reference to right before and after graft modification
The change of phenylenediamine age resistor quality calculates grafting rate as 29.1%.
Embodiment 5：
(1) age resistor dispersion liquid：2.66g (0.01mol) N cyclohexyl N' phenyl P phenylene diamine (4010) is added
In 200ml acetone, the ultrasonic disperse 1h under normal temperature, uniform age resistor dispersion liquid is obtained；
(2) monomer graft reaction：The age resistor dispersion liquid obtained in step (1) is transferred to three with condensing unit
In mouth bottle, and 0.55g deionized waters and 0.015g hydroquinones are added, keep continuing magnetic force stirring afterwards, be slowly added dropwise
3.053g (0.0215mol) GMA, during dropwise addition, reaction temperature is controlled at 60~70 DEG C；
(3) it is aged：After methacrylate-based monomer drips, continue to stir 30min, then heat to 80~90
DEG C, insulation reaction 12h naturally cools to room temperature afterwards, and extracting, washing, drying connect to GMA
The modified p phenylenediamine type antioxidant of branch.
Obtained glycidyl methacrylate graft is modified p phenylenediamine type antioxidant, with reference to right before and after graft modification
The change of phenylenediamine age resistor quality calculates grafting rate as 26.7%.
Matched by table 1 Suo Shi, production prepares native rubber composite material in conventional manner respectively, and preparation technology flow is：
Natural rubber (NR) → plasticate → zinc oxide, stearic acid → accelerant CZ, altax → age resistor → sulphur (S)；Obtain old
NR composite materials properties before change are as shown in table 2.In order to further investigate ageing-resistant performance, 100 °C in ageing oven
Lower thermo-oxidative ageing is handled 72 hours, and it is as shown in table 3 to obtain the NR composite materials properties after aging.
The rubber experiment of table 1. matches
| Embodiment | Control 1 | Control 2 | 1 | 2 | 3 | 4 | 5 |
| NR | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Zinc oxide | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Stearic acid | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Carbon black N330 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| Accelerant CZ | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Altax | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant 4010 | 1 | --- | --- | --- | --- | --- | --- |
| Antioxidant 4010NA | --- | 1 | --- | --- | --- | --- | --- |
| Modification-antioxidant 4010 NA | --- | --- | 1 | 1 | 1 | --- | --- |
| Modification-antioxidant 4010 | --- | --- | --- | --- | --- | 1 | 1 |
| Sulphur（S） | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
Before the thermo-oxidative ageing of table 2., the mechanical property of NR composites
| Embodiment | Blank 1 | Blank 2 | 1 | 2 | 3 | 4 | 5 | Remarks |
| Tensile strength/MPa | 27.48 | 27.92 | 29.15 | 30.35 | 30.71 | 29.90 | 31.26 | GB/T528-1998 |
| Elongation at break/% | 549.24 | 558.08 | 607.60 | 600.68 | 590.85 | 619.40 | 588.78 | GB/T528-1998 |
| 300% stress at definite elongation/MPa | 9.80 | 9.39 | 10.82 | 11.08 | 11.20 | 10.98 | 11.34 | GB/T528-1998 |
| Tearing strength/KNm-1 | 45.85 | 42.46 | 49.65 | 53.68 | 56.55 | 47.85 | 52.92 | GB/T529-1999 |
| Shao's A hardness | 52 | 52 | 53 | 54 | 54 | 53 | 54 | GB/T531-1999 |
After the thermo-oxidative ageing of table 3., the mechanical property of NR composites
| Embodiment | Blank 1 | Blank 2 | 1 | 2 | 3 | 4 | 5 | Remarks |
| Tensile strength/MPa | 18.86 | 19.40 | 20.84 | 22.15 | 23.34 | 21.56 | 23.07 | GB/T528-1998 |
| Elongation at break/% | 311.42 | 320.78 | 359.70 | 366.41 | 371.05 | 372.29 | 367.40 | GB/T528-1998 |
| 300% stress at definite elongation/MPa | 6.76 | 6.52 | 7.73 | 8.09 | 8.51 | 7.92 | 8.37 | GB/T528-1998 |
| Shao's A hardness | 60 | 60 | 61 | 62 | 62 | 61 | 62 | GB/T531-1999 |
Note：1 sample is compareed in table 1 and with the addition of 1 part of antioxidant 4010；Compare 2 samples and with the addition of 1 part of antioxidant 4010NA；
The glycidyl methacrylate graft that the sample of embodiment 1 ~ 3 with the addition of prepared by 1 part respectively is modified antioxidant 4010NA；It is real
Apply the glycidyl methacrylate graft that example 4 ~ 5 with the addition of prepared by 1 part respectively and be modified antioxidant 4010.
Claims (6)
1. a kind of preparation method of rubber antioxidant, it is characterised in that comprise the following steps:(1) age resistor dispersion liquid：Will
Age resistor is N- isopropyl-N'- diphenyl-para-phenylene diamines, N- cyclohexyl-N'- phenyl -1,4- p-phenylenediamine, N,
Bis--iso-octyl of N'- p-phenylenediamine, N, N'- bis- (2- naphthyls) p-phenylenediamine, N, N'- DTPD di tolyl p phenylenediamines or
N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamines are added in organic solvent, and ultrasonic disperse is uniform under normal temperature, obtains
To age resistor dispersion liquid；(2) monomer graft reaction：Add in the age resistor dispersion liquid obtained under agitation to step (1)
Enter water and polymerization inhibitor, GMA is added dropwise after stirring, reaction temperature is controlled at 60~70 DEG C；
(3) it is aged：After GMA drips, continue to stir more than 20min, then heat to 80~
90 DEG C, insulation reaction 11-13h, room temperature is cooled to afterwards, product is obtained after extracting, washing, drying.
A kind of 2. preparation method of rubber antioxidant as described in claim 1, it is characterised in that：The age resistor and first
The mol ratio of base glycidyl acrylate is 1:2.05~2.15.
A kind of 3. preparation method of rubber antioxidant as described in claim 1, it is characterised in that：The use of the polymerization inhibitor
Measure as the 1% ~ 5% of age resistor quality, the dosage of water is the 10% ~ 20% of age resistor quality.
A kind of 4. preparation method of rubber antioxidant as described in claim 1 or 3, it is characterised in that：The polymerization inhibitor
For hydroquinones, hydroquinones monobutyl ether, tert-butyl catechol, 2- TBHQs or 2,5- di-t-butyls pair
One kind of benzenediol.
A kind of 5. preparation method of rubber antioxidant as described in claim 1 or 3, it is characterised in that：Described water
For deionized water.
A kind of 6. preparation method of rubber antioxidant as described in claim 1, it is characterised in that：The organic solvent is
Acetone, toluene, ethyl acetate, dichloromethane, methanol, ethanol, the one or more of acetonitrile or tetrahydrofuran.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110156919B (en) * | 2018-02-10 | 2020-07-28 | 北京化工大学 | Rubber antioxidant and preparation method thereof |
| CN110343207B (en) * | 2018-04-03 | 2021-01-12 | 北京化工大学 | Rubber anti-aging agent using styrene-GMA copolymer as carrier and preparation method thereof |
| CN111825898B (en) * | 2019-04-18 | 2022-06-28 | 北京化工大学 | Rubber anti-aging agent and preparation method thereof |
| CN112143026B (en) * | 2019-06-28 | 2021-12-24 | 北京化工大学 | Modified rubber antioxidant, composition containing same, preparation method and application thereof |
| CN113956538A (en) * | 2020-07-20 | 2022-01-21 | 北京化工大学 | Novel anti-aging agent and preparation method and application thereof |
| CN115260585B (en) * | 2021-04-30 | 2023-12-22 | 北京化工大学 | Anti-aging agent composition and preparation method and application thereof |
| CN115368253B (en) * | 2021-05-21 | 2023-12-15 | 北京化工大学 | Rubber anti-aging agent containing double-p-phenylenediamine structure, preparation method, composition and application |
| CN115536913B (en) * | 2022-10-12 | 2024-04-16 | 科迈特新材料有限公司 | Heat-resistant and aging-resistant modifier for rubber and preparation method thereof |
| CN117962380B (en) * | 2024-03-29 | 2024-06-11 | 烟台富利新材料科技有限公司 | Method for preparing polypropylene synthetic paper by adopting organic pearlescent master batch |
| CN118061637A (en) * | 2024-04-18 | 2024-05-24 | 烟台富利新材料科技有限公司 | Polyethylene-polypropylene blended biaxially oriented synthetic paper and preparation method thereof |
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