CN106750666B - A kind of preparation method and applications of plant polyphenol base rubber accelerator - Google Patents
A kind of preparation method and applications of plant polyphenol base rubber accelerator Download PDFInfo
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/72—2-Mercaptobenzothiazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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Abstract
The invention discloses a kind of preparation method and applications of plant polyphenol base rubber accelerator, (1) will promote the secondary amine of base to be dissolved in formaldehyde ethanol solution to stir containing rubber；(2) return stirring in sour water bath is adjusted；(3) plant polyphenol is added in absolute ethyl alcohol, adjusting sour sonic oscillation, the reaction was continued；(4) by reaction product in stand at low temperature, filtering；(5) distilled water is added in filtrate, plant polyphenol Quito function promoter is precipitated, washing, filters, dries to get final product.Collection promotes the vulcanization of rubber, white carbon surface modified and prevents the multiple actions such as ageing of rubber and one, it is a kind of Multifunctional rubber accelerating agent, have the characteristics that environmental-friendly, the preparation condition of the multifunctional assistant is mild, and byproduct of reaction is few, and yield is high, it is at low cost, the requirement for meeting " green chemical industry " can should be in green tire tread rubber applied to the strength and extension property and dynamic mechanical that can effectively improve rubber in silica compound.
Description
Technical field
The invention belongs to the preparation method technical fields of accelerating agent, and in particular to a kind of plant polyphenol base rubber accelerator
Preparation method and applications.
Background technology
Rubber chemicals are the important auxiliary materials of rubber industry.By traditional classification, rubber chemicals are divided into vulcanization aid, protection
Auxiliary agent, processing aid and other four major class of special functional rubber chemicals.In rubber industry, although auxiliary dosage is relatively very
It is small, but very important effect is played to product processing and the improvement of application performance.The development of rubber chemicals gradually shows height
The features such as relative molecular mass, multi-functional, high-performance, greenization, Composite.
Thiofide is a kind of very important rubber processing aids, and traditional rubber accelerator only serves promotion
Vulcanization of rubber crosslinking, the effect for shortening vulcanization time.In sulfidation, the functional group of vulcanization accelerator takes part in vulcanization instead
It answers, forms the suspension side chain in vulcanization reaction later stage, these pendent groups do not have the raising of rubber composite material performance
The help of benefit.And these rubber tradition accelerating agents can also migrate or release in use toxic small molecule, band
Carry out environmental pollution.Therefore exploitation " one multipotency ", " environment-friendly high-efficiency " the multi-functional accelerating agent of rubber be rubber chemicals field very
Important research contents.
Into in the 1990s, internationally famous tyre company Goodyear, Michelin, Bridgeston etc. are pushed away in succession
" green tire " (or fuel-saving tire) to save fuel oil and reduce exhaust gas discharge as purport is gone out, with common radial phase
Energy consumption than green tire is greatly reduced.Thus greatly developing for " green tire " has greatly pushed the hair of " Green Additives "
Exhibition.Prepare the developing direction that environmentally friendly, efficient, multi-functional rubber accelerator is current rubber chemicals both at home and abroad.
White carbon black/solution polymerized butadiene styrene rubber balanced constant is the common ligand for preparing High-performance green tire tread glue at present
System, but white carbon grain size is small, and surface polarity with the poor compatibility of rubber, therefore easily reunites greatly and is difficult to disperse.Therefore white carbon
Surface is needed to be modified, stuffing surface modification agent usually used at present includes titanate coupling agent and silane coupling agent etc..But this
There are generate small molecule and poor storage stability to the surface modifier of a little small molecules in poor processability, modifying process.
It develops with promoting the vulcanization of rubber and improve the Multifunctional rubber accelerating agent of white carbon-rubber interface effect to cause that people's is wide
General concern.
Since the accelerating agent containing secondary amine will produce carcinogen nitrosamine in sulfidation, exist to health latent
It is threatening.Therefore in recent ten years, external several top auxiliary agent manufacturers input substantial contributions and technical force's exploitation at
Work(some be free of nitrosamine or the accelerating agent new varieties to nitrosamine safety, the more representational N- for having Flexsys companies
The double benzothiazole sulfenamides (TBSI) of tertiary butyl -2-, bis- (2-[4-morpholinodithio) the secondary sulphonyl of N- cyclohexyl-of Uniroyal companies
The N- oxygen diethylidene sulphide amino formyl-N- tert. butyl sulphenamides of amine (ESVE or CBSA) and Goodyear companies
(OTTOS), these sulfenamide type accelerators can be used as the substitute use of NOBS, DIBS and OTOS.Flexsys companies develop
Two hydration six methines, 1,6 pairs of thiosulfuric acid disodiums (i.e. DHTS or HTS) of success, can form flexible hybrid cross-linked network.This
Kind cross-linked structure can inhibit the variation of cross-linked structure and crosslink density caused by over cure, high temperature vulcanized and anoxybiotic aging, Jin Erfang
It is only deteriorated with related physical property of reverting and dynamic property declines.But these accelerating agents being modified, which still have, to be had a single function
Disadvantage, and molecular weight is low, is easily precipitated.
White carbon black/solution polymerized butadiene styrene rubber balanced constant is the common ligand for preparing High-performance green tire tread glue at present
System, therefore develop the extensive concern for causing people for the multifunctional assistant of white carbon system.Patent 200810220321.7 will
2- benzothiazolyl mercaptans and alkali soluble in organic solvent, then be added chlorocarbon base silane, it is reacted be prepared for collection promote vulcanization,
The Multifunctional rubber processing aid of the functions such as plasticising and reinforcement.Patent 201210013339.6 is sweet by coupling agent γ-shrink
Oily ether propyl trimethoxy silicane reacts under certain condition with mutual-amido two polyaniline (PPDA), is prepared for white carbon surface
Novel multifunctional additive that is modified and preventing ageing of rubber double action.Willow face etc. synthesizes two kinds of rare earth rubber accelerating agent paddy
Propylhomoserin aminodithioformic acid lanthanum (La-GDTC) and N- phenyl-N'- (γ-triethoxysilane)-propyl-thiocarbamide (STU), knot
Fruit finds that both rare earth accelerating agents have the double action for improving curingprocess rate and improving filler-rubber interface.These are prepared
Method and process is all harsher, and production cost is higher, and molecular weight product is low, it is difficult to improve dosage it is big when be easily precipitated lack
Point.
Invention content
Accelerating agent presence for modification existing in the prior art has a single function and molecular weight is low, and the technology being easily precipitated is asked
Topic, the purpose of the present invention is to provide a kind of preparation method and applications of plant polyphenol base rubber accelerator, wherein plant is more
The preparation method of phenolic group Multifunctional rubber accelerating agent includes selection, proportioning, reaction temperature, time and the pH value etc. of raw material, and
The separation of product, method of purification.Plant polyphenol Quito functional rubber is promoted into the technology applied to rubber, including addition component,
Method etc. and addition sequence (being added with together with white carbon).One kind is specifically related to using plant polyphenol as matrix, using " one pot two
Footwork " prepares plant polyphenol Quito function promoter, and preparing has " promoting the vulcanization of rubber ", " modification of white carbon surface " and " prevent
The multi-functional application technology with integrated rubber processing aids and the New-type adjuvant in silica compound such as only aging ".
The technical solution that the present invention takes is：
A kind of preparation method of plant polyphenol base rubber accelerator, which is characterized in that specifically comprise the following steps：
(1) it by a certain amount of secondary amine for promoting base containing rubber, is dissolved in the ethanol solution of 100ml formaldehyde, formaldehyde：
The volume ratio of ethyl alcohol is 6:94ml/ml, secondary amine quality：The mass volume ratio of anhydrous ethanol solvent is 1：5-10g/ml, stirring
10-20min makes mixture fully dissolve；
(2) it is adjusted with acid PH=3-6, mixture is placed in the three-necked flask of 500ml specifications, in 70-90 DEG C of water-bath
Condensing reflux stirs 3-6h, and heating stirring makes formaldehyde fully be reacted with secondary amine；
(3) a certain amount of plant polyphenol is added in absolute ethyl alcohol, plant polyphenol：The mass volume ratio of anhydrous ethanol solvent
It is 1:5-10g/ml is adjusted with acid pH value 3-6, sonic oscillation 5min；Plant polyphenol ethanol solution is added prepared by step (2)
The reaction was continued in solution 3-9h；Plant polyphenol fully participates in reacting, and completes the synthesis of novel accelerating agent jointly, molten in reaction process
Liquid color is gradually transparent；
(4) by reaction product at -10 DEG C stand at low temperature 2 days, make unreacted imines be precipitated, filtrate is obtained by filtration；
(5) by distilled water and filtrate by volume 4:1 ratio mixes, and plant polyphenol Quito function promotes in mixed process
Agent is precipitated, and then washes 3 times, filters, 60 DEG C of drying 6h are to get final product.
Further, it is 2-steryl benzothiazole or the tertiary fourths of N- to promote the secondary amine of base containing rubber in the step (1)
Base -2-[4-morpholinodithio sulfenamide.
Further, final product obtained is plant polyphenol base rubber accelerator in the step (5), and molecular weight is
611-682。
Further, 1-3phr plant polyphenol base rubber accelerators are replaced to the accelerating agent in former rubber compounding.Above-mentioned system
Accelerating agent made from Preparation Method is applied to the preparation method of rubber, which is characterized in that specifically comprises the following steps：
(1) mixing：By plant polyphenol Quito functional rubber accelerating agent and white carbon in mass ratio 1:12.5 being added to together
In mixer, 70-90 DEG C of mixing a period of time 10min of control melting temperature, it is therefore an objective to make sizing material be carried out with filler material tentatively mixed
It closes；
(2) mill：Sizing material after mixing is subjected to tabletting on a mill, the sulphur of blend glue stuff mass ratio 0.9% is added
Huang, it is thin 6 times logical as the crosslinking agent of the vulcanization of rubber, bottom sheet after triangle bag is beaten, rubber compound is obtained；
(3) it measures：The glue that 5g or so is cut off on rubber compound, be placed on vulcameter set the vulcanization time of rubber compound as
90s；
(4) it shapes：It will vulcanize under the certain temperature and pressure of rubber compound, obtain vulcanizate.
Further, the temperature in the step (4) is 160 DEG C, and pressure is 10M Pa, and vulcanization time determines for vulcameter
Time be 90s.
Beneficial effects of the present invention are：
The present invention uses bio-based materials plant polyphenol for primary raw material, is prepared for the multi-functional rubber for silica compound
Promoter for rubber.
The Multifunctional rubber accelerating agent of the present invention has the following advantages：
1. collection promotes, the vulcanization of rubber, white carbon surface is modified and prevents the multiple actions such as ageing of rubber and one, is a kind of
Multifunctional rubber accelerating agent.
2. plant polyphenol is a kind of biomaterial, derive from naturally, therefore the multifunctional assistant has environmental-friendly spy
Point.
3. the preparation condition of the multifunctional assistant is mild, byproduct of reaction is few, and yield is high, at low cost, meets " greenization
The requirement of work ".
4., can Ying Yu applied to the strength and extension property and dynamic mechanical that can effectively improve rubber in silica compound
In green tire tread rubber.
5. dialogue carbon blacksurface can be modified to a certain extent applied in silica compound, the reinforcement of white carbon is improved
Effect.
The Multifunctional rubber accelerating agent of the present invention is applied in rubber, has the advantage that：
1. the accelerating agent in original formulation can be replaced completely or partially, there is higher curing efficiency, while improving vulcanization
The crosslink density of glue.
2. the interaction of white carbon-rubber can be improved, the dispersion of white carbon is improved, to improve strong the stretching property of rubber
Energy.
3. having certain anti-aging effect, the service life of rubber is improved.
4., can should be in green tire tire applied to the dynamic mechanical that can effectively improve rubber in silica compound
In the glue of face.
5. the time of scorch applied to vulcanizate in silica compound increases, the vulcanized rubber improved to a certain extent
Processed safely performance.
Description of the drawings
Fig. 1 is the infrared spectrogram of TPM in the present invention.
Fig. 2 is the infrared spectrogram of TPN in the present invention.
Fig. 3 is influence diagrams of the TPM and TPN to SSBR2557A rubber vulcanization characteristics.
Specific implementation mode
The preparation of 1 plant polyphenol base rubber accelerator TPM of embodiment
A kind of preparation method of plant polyphenol base rubber accelerator, specifically comprises the following steps：
(1) 10g 2-steryl benzothiazole (MBT) is weighed, is dissolved in the ethanol solution of 50ml formaldehyde, stirs at room temperature
10min；
(2) PH=3, the return stirring 6h in 70 DEG C of water-baths are adjusted with hydrochloric acid；
(3) 10g plant polyphenols are added in 50ml absolute ethyl alcohols, PH=3, sonic oscillation 5min is adjusted with hydrochloric acid；
(4) plant polyphenol ethanol solution in step (3) is added in solution prepared by step (2), is continued at 70 DEG C anti-
Answer 9h；
(5) by reaction product at -10 DEG C stand at low temperature 2 days, make unreacted MBT be precipitated, filtering；
(6) distilled water is added in filtrate, plant polyphenol Quito function promoter is precipitated, and then washes 3 times, filters, 60 DEG C
6h is dried to get final product, form is light brown powder TPM, yield 67%.
The preparation of 2 plant polyphenol base rubber accelerator TPN of embodiment
A kind of preparation method of plant polyphenol base rubber accelerator, specifically comprises the following steps：
(1) 10g N tert butyl benzothiazole 2 sulfenamides (NS) are weighed, are dissolved in the ethanol solution of 100ml formaldehyde,
10min is stirred at room temperature；
(2) PH=4, the return stirring 3h in 80 DEG C of water-baths are adjusted with hydrochloric acid；
(3) 10g plant polyphenols are added in 100ml absolute ethyl alcohols, PH=4, sonic oscillation 5min is adjusted with hydrochloric acid；
(4) plant polyphenol ethanol solution in step (3) is added in solution prepared by step (2), is continued at 80 DEG C anti-
Answer 5h；
(5) by reaction product at -10 DEG C stand at low temperature 2 days, make unreacted NS be precipitated, filtering；
(6) distilled water is added in filtrate, plant polyphenol Quito function promoter is precipitated, and then washes 3 times, filters, 80 DEG C
6h is dried to get final product, form is light brown powder TPN, yield 70.7%.
The preparation of 3 plant polyphenol base rubber accelerator TPM of embodiment
A kind of preparation method of plant polyphenol base rubber accelerator, specifically comprises the following steps：
(1) 10g 2-steryl benzothiazole (MBT) is weighed, is dissolved in the ethanol solution of 100ml formaldehyde, stirs at room temperature
10min；
(2) PH=6, the return stirring 3h in 90 DEG C of water-baths are adjusted with hydrochloric acid；
(3) 10g plant polyphenols are added in 100ml absolute ethyl alcohols, PH=6, sonic oscillation 5min is adjusted with hydrochloric acid；
(4) plant polyphenol ethanol solution in step (3) is added in solution prepared by step (2), is continued at 90 DEG C anti-
Answer 3h；
(5) by reaction product at -10 DEG C stand at low temperature 3 days, make unreacted MBT be precipitated, filtering；
(6) distilled water is added in filtrate, plant polyphenol Quito function promoter is precipitated, and then washes 3 times, filters, 60 DEG C
6h is dried to get final product, form is light brown powder TPM, yield 74.6%.
The structural characterization of embodiment 4TPM and TPN
Using fourier transform infrared spectroscopy (FTIR) to the TPM and embodiment that are synthesized in the embodiment 1 of synthesis and 3
The TPN synthesized in 2 carries out structural characterization.
The infrared curve of TP can be seen that 3200~3600cm from Fig. 1-1Belong to stretching for O-H keys in tea polyphenols (TP)
Contracting vibration, 1200cm-1For the absorption peak of tea polyphenols C-O keys.Fig. 1 TPM and figure TP are subjected to comparison discovery, TPM is in 1650-
2000cm-1There is the quartet of phenyl ring in place, and in 3200~3600cm-1There is wide absorption peak at place, belongs to tea polyphenols O-H keys
Stretching vibration, 1200cm-1There is a small absorption peak at place, can belong to tea polyphenols C-O keys.It to sum up analyzes, certain features of TPM
Absorption peak is consistent with some characteristic peaks of captax, while also some essential characteristic peaks containing TP, in conclusion having prepared
Go out new rubber chemicals TPM.
It can be seen that being located at 3300cm from the IR curves of NS in Fig. 2-1Left and right is the characteristic peak of NH, 3050cm-1Left and right
Small peak is the stretching vibration of aromatic ring, 2920cm-1Peak is the stretching vibration for being saturated C-H, 1450cm-1、1420cm-1Left and right is virtue
The skeleton stretching vibration of ring, 754cm-1Left and right is that the ortho position two on aromatic ring replaces characteristic absorption.
The IR curves of TPN can be seen that 3200~3600cm from Fig. 2-1Belong to the flexible of O-H keys in tea polyphenols (TP)
Vibration, 1200cm-1For the absorption peak of tea polyphenols C-O keys.In 754cm-1Left and right is that the ortho position two on aromatic ring replaces feature to inhale
It receives, this is the characteristic absorption peak of phenyl ring, and originally accelerator NS is in 3300cm-1NH characteristic peaks disappear, and illustrate that accelerator NS and tea are more
Phenol reacts Mannich reaction, and TPN is successfully prepared out.
5 plant polyphenol base rubber accelerator of embodiment is applied to the preparation method of rubber
(1) it is kneaded：137.5g ESSBR2535E are added in mixer, then 50g white carbons, 5g plant polyphenol bases are promoted
It is added in mixer together into agent TPM and Si69 4g, auxiliary material zinc oxide 3g, stearic acid 1g, DPG 1.5g is added, close
10min is mixed in mill.Above-mentioned mixing initial temperature is 70 DEG C, is kneaded 70 turns/min of rotating speed, and mixing total time is 8min；
(2) mill：Sizing material after mixing is subjected to tabletting on a mill, addition 1.76g Sulfurs are thin 6 times logical, beat triangle
Bottom sheet after packet；
(3) vulcanization sizing：It will vulcanize under 160 DEG C of rubber compound, 10MPa pressure, vulcanization time is to be determined by vulcameter
Technique sulfurizing time t90, you can obtain vulcanizate.
6 plant polyphenol base rubber accelerator of embodiment is applied to the preparation method of rubber
(1) it is kneaded：137.5g ESSBR2535E are added in mixer, then 50g white carbons, 5g plant polyphenol bases are promoted
It is added in mixer together into agent TPN and Si69 4g, auxiliary material zinc oxide 3g, stearic acid 1g, DPG 1.5g is added, close
10min is mixed in mill.Above-mentioned mixing initial temperature is 70 DEG C, is kneaded 70 turns/min of rotating speed, and mixing total time is 8min；
(2) mill：Sizing material after mixing is subjected to tabletting on a mill, addition 1.76g Sulfurs are thin 6 times logical, beat triangle
Bottom sheet after packet；
(3) vulcanization sizing：It will vulcanize under 160 DEG C of rubber compound, 10MPa pressure, vulcanization time is to be determined by vulcameter
Technique sulfurizing time t90, you can obtain vulcanizate.
Reference examples using prior art Central Plains rubber compounding it is traditional captax substitution embodiment 5 and 6 in TPM or
The vulcanization characteristics curve of TPN, rubber compound are as shown in Figure 3.
From figure 3, it can be seen that curingprocess rates and traditional captax (reference examples) of the TPM and TPN to white carbon is added
The activity of vulcanization is promoted to be not much different, and the highest torque of vulcanizate is all higher than the sizing material of reference examples, this illustrates TPM and TPN
The crosslink density of vulcanizate can be improved.
The physical mechanical property of vulcanizate is as shown in table 1.
The influence of table 1TPM, TPN to vulcanized mechanical
From table 1 it follows that compared to control group, the tensile strength of TPM and TPN vulcanizates, is broken and is stretched tearing strength
Long rate and hardness all increase.Illustrate that TPM and TPN dialogue carbon blacksurface can be modified to a certain extent, improves white carbon
Strengthening action.And at 100 DEG C after aging 48h, the stretching strength retentivity of TPM and TPN vulcanizates is above control group, says
Bright TPM and TPN also has the effect for preventing ageing of rubber.
The basic principle of the present invention is as follows：
Plant polyphenol is the general name of more than the 30 kinds of Polyphenols and its derivative that are extracted from plant, is had on its strand rich
Rich hydroxyl has higher molecular weight and wider molecular weight distribution.Technical grade other plant polyphenol is from plant, trees
It is extracted in skin, root, leaf, therefore cost is relatively low.It is 432 left to have a large amount of phenolic hydroxyl group, average molecular weight in plant polyphenol structure
The right side, will be big than general traditional rubber accelerator.Phenolic hydroxyl group on plant polyphenol can form hydrogen with the hydroxyl on white carbon
Key and free radical can be adsorbed, can be used as the surface modifier and anti-aging agent of white carbon, there are the potentiality applied in rubber.
This paper is by plant polyphenol and formaldehyde, imines rubber accelerator (2-steryl benzothiazole or N- tertiary butyls -2-[4-morpholinodithio
Sulfenamide) reaction is prepared for new Multifunctional rubber accelerating agent, multi-functional accelerating agent collection " promoting the vulcanization of rubber ", " hard charcoal
Black surface is modified " and " preventing ageing of rubber " etc. it is multi-functional with it is integrated, provided for the excellent green tire of processability multi-functional
Natural, green, efficient New Processing Aid provide practical basis.
This project is based on plant polyphenol and is rich in phenolic hydroxyl group, and phenolic hydroxyl group faces the more active premise of benzene ring hydrogen,
Under acid catalysis, phenolic hydroxyl group, which faces a benzene ring hydrogen, Mannich addition reaction occurs with formaldehyde, secondary amine (or ammonia).Pass through choosing
The secondary amine (such as 2-steryl benzothiazole or N tert butyl benzothiazole 2 sulfenamide) for promoting base with rubber is selected, just
Plant polyphenol base rubber accelerator can be prepared.And the phenolic hydroxyl group retained on plant polyphenol base rubber accelerator can with it is white
Hydroxyl on carbon black forms hydrogen bond and can adsorb free radical, thus have the surface modifier that can be used as white carbon and it is anti-always
Agent.Therefore the tea-polyphenol base rubber accelerator has " promoting the vulcanization of rubber ", " modification of white carbon surface " and " prevents rubber simultaneously
The functions such as aging ".It is a kind of environmentally protective Multifunctional rubber processing aid.
The above is not limitation of the present invention, it should be pointed out that：Those skilled in the art are come
It says, under the premise of not departing from essential scope of the present invention, several variations, modifications, additions or substitutions can also be made, these improvement
Protection scope of the present invention is also should be regarded as with retouching.
Claims (4)
1. a kind of preparation method of plant polyphenol base rubber accelerator, which is characterized in that specifically comprise the following steps：
（1）By a certain amount of secondary amine for promoting base containing rubber, it is dissolved in the ethanol solution of 100ml formaldehyde, formaldehyde：Ethyl alcohol
Volume ratio be 6:94 ml/ml, secondary amine quality：The mass volume ratio of anhydrous ethanol solvent is 1：5-10 g/ml stir 10-
20min makes mixture fully dissolve；
（2）It is adjusted with acid pH=3-6, mixture is placed in three-necked flask, condensing reflux stirs 3-6h in 70-90 DEG C of water-bath,
Heating stirring makes formaldehyde fully be reacted with secondary amine；
（3）A certain amount of plant polyphenol is added in absolute ethyl alcohol, plant polyphenol：The mass volume ratio of anhydrous ethanol solvent is 1:
5-10 g/ml are adjusted with acid pH value 3-6, sonic oscillation 5min；Step is added in plant polyphenol ethanol solution（2）What is prepared is molten
The reaction was continued in liquid 3-9h；Reaction is gradually transparent to solution colour；
（4）By reaction product at -10 DEG C stand at low temperature 2 days, make unreacted imines be precipitated, filtrate is obtained by filtration；
（5）By distilled water and filtrate by volume 4:1 ratio mixes, and plant polyphenol base rubber accelerator is analysed in mixed process
Go out, then wash 3 times, filters, 60 DEG C of drying 6h are to get final product；
The step（1）In containing rubber promote base secondary amine be 2-steryl benzothiazole or N- tertiary butyls -2-[4-morpholinodithio
Sulfenamide；
The step（5）In final product obtained be plant polyphenol base rubber accelerator, molecular weight 611-682.
2. application of the accelerating agent made from preparation method in rubber according to claim 1, which is characterized in that by 1-3phr
Accelerating agent in the former rubber compounding of plant polyphenol base rubber accelerator substitution.
3. accelerating agent made from preparation method is applied to the preparation method of rubber according to claim 1, which is characterized in that tool
Body includes the following steps：
（1）Mixing：By plant polyphenol base rubber accelerator and white carbon in mass ratio 1:12.5 are added in mixer together, control
70-90 DEG C of mixing 10min of melting temperature processed, makes sizing material tentatively be mixed with filler material；
（2）Mill：Sizing material after mixing is subjected to tabletting on a mill, the Sulfur of blend glue stuff mass ratio 0.9% is added, is made
It is thin 6 times logical for the crosslinking agent of the vulcanization of rubber, bottom sheet after triangle bag is beaten, rubber compound is obtained；
（3）It measures：The glue that 5g or so is cut off on rubber compound is placed on vulcameter the vulcanization time for setting rubber compound as 90s；
（4）Sizing：It will vulcanize under the certain temperature and pressure of rubber compound, obtain vulcanizate.
4. accelerating agent is applied to the preparation method of rubber according to claim 3, which is characterized in that the step（4）In
Temperature is 160 DEG C, and pressure is 10M Pa, and vulcanization time is the time 90s that vulcameter determines.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611034924.9A CN106750666B (en) | 2016-11-22 | 2016-11-22 | A kind of preparation method and applications of plant polyphenol base rubber accelerator |
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