CN109320774A - A kind of method that natural astaxanthin and its esters are carried on filler proof rubber composite material aging - Google Patents
A kind of method that natural astaxanthin and its esters are carried on filler proof rubber composite material aging Download PDFInfo
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- CN109320774A CN109320774A CN201811204178.2A CN201811204178A CN109320774A CN 109320774 A CN109320774 A CN 109320774A CN 201811204178 A CN201811204178 A CN 201811204178A CN 109320774 A CN109320774 A CN 109320774A
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- filler
- esters
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- natural astaxanthin
- rubber composite
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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
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- C—CHEMISTRY; METALLURGY
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
A kind of natural astaxanthin is invented and its method that esters are carried on filler proof rubber composite material aging, specifically first natural astaxanthin and its esters are dissolved in organic solvent, gum filler is added to stir and dry to constant weight, it is finally added to that rubber composite material is made in rubber, wherein natural astaxanthin and its esters account for the 0.1%~10% of filler.Natural astaxanthin and its esters are carried on filler as free radical scavenger, it is then added in rubber, improve the ageing properties such as thermo-oxidative stability, the photooxidation stability of rubber composite material, delay the aging of rubber composite material, service life during extending its processing, storage and in product use process, and due to being carried on filler, dispersibility is more preferable, has better anti-aging effect compared to the addition of direct mechanical blending formula.The present invention opens a new field for the application of natural astaxanthin and its esters, and also the aging for proof rubber composite material provides new material and method.
Description
Technical field
The present invention relates to the preparation methods of rubber composite material, load more particularly, to a kind of natural astaxanthin and its esters
In the method for filler proof rubber composite material aging.
Background technique
Rubber composite material is due to combining the high resiliency of rubber, good insulating properties and the high-modulus of reinforcement and filler material
The advantages that strong with designability, thus it is widely used in the every field such as industry, agricultural, building, traffic, medicine, life.So
And relative to other traditional materials such as ceramic material and metal material, the performance of rubber composite material in processing, store or make
With in the process, vulnerable to the influence and effect of external environmental factor, there is performance and gradually degenerate, or even loses use value, i.e. rubber
Glue aging.Thus the aging of proof rubber composite material has important practical significance.
Cause the principal element of rubber composite material aging that can be divided into two aspects of internal factor and external factor.It is inherent because
Element is mainly that rubber belongs to a kind of high-molecular organic material, between the chemical bond energy of molecule, the bond energy and macromolecular of cross-linked network
Cohesive energy is all relatively low, is easy by various erosions, destroys and aging.External factor can be divided into three classes, first is that physical factor, such as
Light, heat, electricity, high-energy radiation and mechanical stress etc.；Second is that chemical factor, such as oxygen, ozone, strong oxidizer, inorganic acid, alkali, salt
Aqueous solution and variable valency metal ions etc.；Third is that biological factor, such as microorganism and ant.The oxidation of rubber and ozonization
The destruction caused by rubber is most commonly seen, also most serious.Furthermore the factors such as heat, light, mechanical stress are toward contact to oxidation and ozone
Activation and/or catalytic action are played in change.Studies have shown that rubber composite material aging under light, heat and oxygen or collective effect is one
A autocatalysis process is mainly carried out according to radical reaction course.
In terms of rubber product actual use situation, aging is the result of a variety of internal and external factor comprehensive functions.Such as automotive wheels
Tire during scrolling, on the one hand will contact and react with the oxygen in atmosphere from beginning to end, go back generating period at the same time
Property ess-strain, generate mechanical loss and then heat, heat has activated oxidation reaction again；On the other hand, tire is in outdoor application
Inevitably by sunlight irradiation, wind and sleet elution and ozone attack, it may occur that photooxidation resistance and ozone aging.It removes
Except this, the crown part of tire is because also suffering from the puncture of the Unpredictabilities sharp object such as friction and grit with ground face contact and cutting
It cuts, this has played catalysis and facilitation to above-mentioned aging reaction again.These agings as caused by a variety of external causes simultaneously finally make to take turns
Tire loses use value.
For the principal element and agine mechaism for causing rubber composite material aging, in rubber industry many methods by with
Carry out the aging phenomenon of proof rubber composite material.Currently, the method for improving rubber composite material anti-aging property mainly has chemistry
Method and physical method, chemical method are mainly to pass through the chemical structure for improving copolymer, introduce the structure containing stable group, such as use
Vinyl groups containing antioxidant carries out modification by copolymerization to improve the anti ageing property of rubber composite material；Physical laws are main
It is the additives by the way that various raising ageing-resistant performances are added, such as antioxidant and light stabilizer, or in rubber composite material
Surface covering etc. improves the ageing-resistant performance of rubber composite material.Antioxidant wherein is added and light stabilizer is rubber composite wood
Most general in material, most convenient and most economical method, however the anti-aging agent of these traditional rubber composite materials often has one
Fixed toxicity, easy to migrate, the volatile and protective benefits duration is short, has large effect to environment, especially for food
The rubber composite material of grade, therefore seek the rubber composite material anti-aging agent of high-efficiency low-toxicity and explore its application method always
It is the major issue of rubber industry.
Astaxanthin, also known as astaxanthin are also known as astacin in Hong Kong & Taiwan areas, be from river crayfish shell, oyster, salmon,
A kind of Red carotenoids found in algae, chemical name are 3,3 '-dihydroxy -4,4 '-diketo-β, β '-carrotene,
It in vivo can be in conjunction with protein and in green, blue.Nature astaxanthin is generated by algae, bacterium and phytoplankton object.
Some water biological species, the shellfish including shrimp, crab all eats these algae and planktonic organism, then this pigment
It is stored in shell, then their appearance presents red.These shellfish again by fish (salmon, trout plus sharp fish) and
Bird (flamingo, crested ibis) predation, is then stored in pigment in skin and adipose tissue.Here it is salmon and some other dynamic
Red reason is presented in object.Hua Zhong Agriculture University professor also studies confirmation: the red color components of neutral red core duck's egg are also natural shrimp
Green element.Natural astaxanthin is that the mankind have found the strongest antioxidant of nature so far, and antioxidant activity is considerably beyond now
Some antioxidants.Its ability for removing free radical is 6000 times of ascorbic effect；It is 1000 times of vitamin E；It is auxiliary
800 times of enzyme Q10；It is nitric oxide production 1800 times；It is 3100 times of natto；It is 700 times of anthocyanidin；It is beta carotene function
110 times of effect；It is 1100 times of nucleic acid effect；It is 1800 times of lycopene effect；It is 800 times of lutein effect；It is tea
320 times of polyphenol effect；Only algae and saccharomycete and bacterium etc. can produce astaxanthin, and more high animal cannot be converted to
This chemical structure.There are one clear features for natural astaxanthin, it is a kind of carotenoids that can uniquely pass through blood-brain barrier
Element.Early in the 1930s, researcher just isolates this special keto-acid carotenoid from the shell of shrimp crab, to 20 generation
It records the eighties, astaxanthin causes people with its brilliant antioxidant activity and the antitumor isoreactivity function of strengthen immunity, anticancer
Extensive concern.
Currently, the production of astaxanthin has artificial synthesized and biological acquisition two ways.Artificial synthesized astaxanthin not only price
Valuableness, and with natural astaxanthin structure, function, application and in terms of significant difference.In configuration aspects, due to two
Hydroxyl (- OH) the optical activity reason at end, astaxanthin have 3S-3 ' S, 3R-3 ' S, 3R-3 ' R (also referred to as left-handed, racemization, dextrorotation)
This 3 kinds of isomery kenels, wherein artificial synthesized astaxanthin be 3 kinds of structure astaxanthins mixture it is (left-handed to account for 25%, dextrorotation and account for
25%, racemization 50% or so), few antioxidant activity, with the intracorporal astaxanthin of aquaculture organisms such as salmon (with transconfiguration-
Based on 3S-3 ' S type) it is completely different.The astaxanthin of yeast bacterium source is 100% dextrorotation (3R-3 ' R), has Partial Antioxidation active；On
Two kinds of source astaxanthins are stated to be used primarily in the coloring of non-edible animal and goods and materials.The astaxanthin in only algae source is 100% left-handed
(3S-3 ' S) structure has strongest biological activity, and large enterprises as FUJI, YAMAHA have passed through years of researches, uses
As the health food, the cosmetics of super quality, drug of the mankind.In terms of physiological function, the stability of artificial synthesized astaxanthin and
Oxidation activity is also lower than natural astaxanthin.Lead to its stability since the hydroxyl (- OH) at astaxanthin molecule both ends can be esterified
Different, 90% or more esterified form of natural astaxanthin exists, therefore more stable, and synthesizing astaxanthin exists with free state, therefore
Stability is different, and synthesizing astaxanthin has to embed and could stablize.Synthesizing astaxanthin due to only have 1/4 or so it is left-handed
Structure, therefore its inoxidizability also only has natural 1/4 or so.In application effect, the bio-absorbable effect of artificial astaxanthin
Also poor compared with natural astaxanthin, when feeding concentration is lower, artificial astaxanthin is green significantly lower than natural shrimp in rainbow trout blood middle concentration
Element, and it can not be converted into native configurations in vivo, the natural astaxanthin of colorability and biological value more than same concentration is low
It is more.In terms of bio-safety, using will inevitably introduce impurity chemical substance when chemical means synthesizing astaxanthin, such as synthesize
Non-natural by-product generated in the process etc. will reduce its biological utilisation safety.It is thus impossible to be used in mankind market.
With the rise of natural astaxanthin, countries in the world are also increasingly tighter to the management of chemical synthesis astaxanthin, such as the U.S.
Food and Drug Administration (FDA) has forbidden chemically synthesized astaxanthin to enter health food market.Currently, the production of astaxanthin
The biological source of exploitation natural astaxanthin is generally tended to, and is thus mass produced.It has the ability to be commercialized cultivation at present
Only 5 national (Japanese FUJI chemical groups < control Sweden, Xia Wei of 7 companies of Haematococcus pluvialis production natural astaxanthin
Yi Liangjia factory >, YAMAHA group, Biogenic company, Cyanotech company of the U.S., Chinese Jingzhou City's natural astaxanthin have
Limit company, Bioprex company of India, Algatech company of Israel), remaining some country and enterprise are greatly all in research and development rank
Section.
Currently, the biological source of natural astaxanthin generally has 3 kinds: waste, the phaffiafhodozyma of processing of aquatic products industry
With microalgae (haematococcus pluvialis).Wherein, content astaxanthin is lower in waste, and extraction is costly, is unsuitable for being advised greatly
Mould production.Natural astaxanthin in phaffiarhodozyma average content is also only 0.40%.In contrast, haematococcus pluvialis Prawn is green
Cellulose content is 1.5%~3.0%, is counted as " concentrate " of natural astaxanthin.
Currently, astaxanthin is mainly used in pharmacy, cosmetics, food, drink as excellent antioxidant and colorant
In product, health care product and aquaculture, have a good application prospect.Such as in pharmaceutical field, EP0786990 is subtracted using astaxanthin
The damage of slow central nervous system and eyes；EP1217996 treats autoimmune disease, chronic filtration venereal disease using astaxanthin
Poison and intracellular bacterial infection；US6335015 uses preventive medicine of the astaxanthin as mazoitis.In cosmetic field,
US6433025 discloses application of the natural astaxanthin in terms of slowing down or preventing ultraviolet light sunburn.In the food industry, publication number
CN105901165A provides a kind of sesame oil and preparation method thereof rich in natural astaxanthin；Publication number CN105767586A is related to
A kind of fortification egg feed of poultry farming and its application；Publication number CN102125093A discloses the cream system of astaxanthin-containing
Product and preparation method thereof.In field of beverage, US6475547 uses astaxanthin in the milk rich in immunoglobulin；Publication number
CN104893932A discloses a kind of compound assembled alcoholic drinks of the oceanic functional with effect of lowering blood sugar；Publication number CN103783614A
Disclose a kind of astaxanthin apple vinegar beverage.In health products trade, KR2000045197 is disclosed containing Chitosan poly oligosaccharide and shrimp
The health-nutrition product of green element；Publication number CN101053409 provides one kind with natural astaxanthin oil, edible fats, natural antioxygen
Agent is raw material, and capsule or tablet containing natural astaxanthin are made of common process；Publication number CN105031314A is disclosed
A kind of marine health capsule with effect of regulating blood fat.In aquaculture field, WO03003848 astaxanthin diester is improved
The growth of cultured fishes；Publication number CN105028996A disclose it is a kind of improve grouper survival rate of seedling additive of bait and
Application method；Publication number CN101999544A provides a kind of rich in the aquaculture composite bait of astaxanthin and its preparation side
Method.
So far, no document report natural astaxanthin and its esters are carried on filler proof rubber composite material aging
Application.Natural astaxanthin and its esters are a kind of natural materials extracted from animals and plants, environment-protecting and non-poisonous, will not be multiple to rubber
Condensation material and environment have adverse effect.
Summary of the invention
It is more toxic for rubber composite material anti-aging agent current in background technique, is easy to migrate, volatile, asking not environmentally
Topic, the purpose of the present invention is to provide safe and environment-friendly, efficiently a kind of natural astaxanthin and its esters are carried on filler protection rubber
The method of glue composite material aging.
Rubber composite material aging under light, heat and oxygen or its collective effect is an autocatalysis process, is mainly pressed
It is carried out according to radical reaction course, and natural astaxanthin and its unique phenolic hydroxyl structure of esters assign its high reproducibility, due to
Natural astaxanthin and its esters are a kind of very strong antioxidant and efficient free radical scavenger, thus by natural astaxanthin and
Its esters is carried on filler and is redispersed in rubber composite material matrix, using natural astaxanthin and its esters be efficiently captured from by
The characteristics of base, can effectively capture the free radical that rubber composite material generates under light, heat and oxygen or its collective effect, thus
The ageing process of rubber composite material can effectively be delayed.
The present invention solve technical problem the technical solution adopted is that:
Natural astaxanthin and its esters are dissolved in organic solvent first, gum filler is added and stirs and do
Dry to be finally added to that rubber composite material is made in rubber to constant weight, wherein natural astaxanthin and its esters account for packing quality point
Several 0.1%~10%.
The natural astaxanthin, scientific name 3,3'- dihydroxy -4,4'- diketo-β, β '-carrotene, molecular formula are
C40H52O4, relative molecular weight 596.86 is a kind of keto-acid carotenoid of non-vitamin A original, and crystal is maroon, fusing point
It is 224 DEG C, insoluble in water, it is dissolved in most of organic solvent.Natural astaxanthin molecule is connected by 4 isoprene double bond head and the tail
Connect, share 11 conjugated double bonds, and in conjugated double bond chain end there are also unsaturated ketone group and hydroxyl, wherein hydroxyl and
Ketone group constitutes alpha-alcohol ketone again, this design feature makes it have more active electronic effect, can to free radical provide electronics or
The unpaired electron for attracting free radical, to remove free radical.
The main source organism of the natural astaxanthin and its esters has: shellfish (such as shrimps), algae are (such as
Haematococcus pluvialis and fungi such as phaffia rhodozyma).
The rubber composite material is native rubber composite material and synthetic rubber composite material.
The filler of the rubber composite material can be divided into reinforcing agent and filler from reinforcing effect.
The filler of the rubber composite material can by sources be divided into organic filler and inorganic filler.
The filler of the rubber composite material can be divided into granular, fibrous, resin-like and sheet by shape.
It is ageing-resistant to improve its in rubber composite material that natural astaxanthin and its esters are carried on applying filler by the present invention
Performance has the following characteristics that
(1) anti-aging agent of traditional rubber composite material is generally by artificial synthesized, often has certain toxicity, no matter from life
It produces, store or to application, all there is large effect to rubber composite material and environment, and natural astaxanthin and its esters are then
It is a kind of natural materials extracted from organism, it is environmentally protective nontoxic, there will not be bad shadow to rubber composite material and environment
It rings, this is of great significance to the anti-aging of the rubber composite material of rubber composite material especially food-grade.
(2) present invention, which using natural astaxanthin and its esters as free radical scavenger is carried on filler and is then added to rubber, answers
Condensation material improves the ageing properties such as thermal stability, photostability, thermo-oxidative stability, the photooxidation stability of rubber composite material, prolongs
The service life of long rubber composite material.And due to being carried on filler, dispersibility is more preferable, adds compared to direct mechanical blending formula
Add with better anti-aging effect.
(3) natural astaxanthin and its esters are due to its own unique physicochemical properties, and efficiently improving, rubber is multiple
While condensation material anti ageing property, it can also assign rubber composite material some other performance, such as anti-microbial property.
Natural astaxanthin and its esters are renewable, sustainable use the natural resources of one kind for being present in nature, this
Invention opens a new application field for the application and development of natural astaxanthin and its esters, also for green high-efficient protects rubber
The aging of glue composite material proposes new method.
Specific embodiment
Below with reference to embodiment and subordinate list, the invention will be further described.
Embodiment 1: the 194.3g natural rubber (SMR10) after plasticating is added in mixer, and setting revolving speed is
70rpm, initial temperature are 90 DEG C, start to be kneaded, the mixture of 97.15g white carbon black and 7.77gSi-69 is added after 2min, be kneaded
The mixture of 9.72g stearic acid, 3.89g zinc oxide, 2.92g accelerator NS is added after 4min, stops mixing, glue after being kneaded 2min
139 DEG C of material temperature degree；Sizing material is put while hot on a mill, setting revolving speed be 15rpm, 55 DEG C of preliminary roller, 50 DEG C of back roller, roller speed ratio
For 1:1.1, roll spacing 1mm, 3 knives are respectively cut in left and right after packet roller, add after 4.27g Sulfur that 3 knives are respectively cut in left and right again, and adjustment roll spacing is
0.2mm starts thin logical and beats triangle bag 6 times, and adjustment roll spacing is that bottom sheet after 1.6mm takes 5g rubber compound in sulphur after placing 12h naturally
Change and measures technique sulfurizing time t on instrument at 150 DEG C90, then (curing temperature is 150 DEG C, vulcanizes for vulcanization on vulcanizing press
Pressure is 10MPa, vulcanization time t90), determine tensile sample and tearing sample respectively with cut-off knife.Heat-resistant air aging property is pressed
GB/T3512-2001 standard is tested, aging temperature be 100 DEG C, the time be respectively for 24 hours, 48h.Rubber is compound before and after aging
The mechanical property parameters of material are as shown in table 1.
The mechanical property of rubber composite material before and after 1 aging of table
1-0: before aging；1-1: aging is for 24 hours；1-2: aging 48h
Embodiment 2: the 193.7g natural rubber (SMR10) after plasticating is added in mixer, and setting revolving speed is
70rpm, initial temperature are 90 DEG C, start to be kneaded, and natural astaxanthin and its esters load that quality is 97.82g are added after 2min
In the compound of white carbon black and the mixture of 7.75gSi-69, be kneaded after 4min be added 9.69g stearic acid, 3.87g zinc oxide,
The mixture of 2.91g accelerator NS stops mixing after being kneaded 2min, and 140 DEG C of sizing material temperature；Sizing material is placed on open mill while hot
On, setting revolving speed is 15rpm, and 55 DEG C of preliminary roller, 50 DEG C of back roller, roller speed ratio is 1:1.1, roll spacing 1mm, and left and right is respectively cut after packet roller
3 knives, add after 4.26g Sulfur that 3 knives are respectively cut in left and right again, and adjustment roll spacing is that 0.2mm starts thin logical and beats triangle bag 6 times, adjustment roll spacing
For bottom sheet after 1.6mm, after placing 12h naturally, 5g rubber compound is taken to measure technique sulfurizing time t at 150 DEG C on vulcameter90,
Then (curing temperature is 150 DEG C, sulfide stress 10MPa, vulcanization time t for vulcanization on vulcanizing press90), with cut-off knife point
Tensile sample and tearing sample are not determined.Heat-resistant air aging property is tested by GB/T3512-2001 standard, aging temperature
Be 100 DEG C, the time be respectively for 24 hours, 48h.The mechanical property parameters of rubber composite material are as shown in table 2 before and after aging.
The mechanical property of rubber composite material before and after 2 aging of table
2-0: unaged；2-1: aging is for 24 hours；2-2: aging 48h
Embodiment 3: the 193.1g natural rubber (SMR10) after plasticating is added in mixer, and setting revolving speed is
70rpm, initial temperature are 90 DEG C, start to be kneaded, and natural astaxanthin and its esters load that quality is 98.48g are added after 2min
In the compound of white carbon black and the mixture of 7.72gSi-69, be kneaded after 4min be added 9.66g stearic acid, 3.86g zinc oxide,
The mixture of 2.90g accelerator NS stops mixing after being kneaded 2min, and 141 DEG C of sizing material temperature；Sizing material is placed on open mill while hot
On, setting revolving speed is 15rpm, and 55 DEG C of preliminary roller, 50 DEG C of back roller, roller speed ratio is 1:1.1, roll spacing 1mm, and left and right is respectively cut after packet roller
3 knives, add after 4.25g Sulfur that 3 knives are respectively cut in left and right again, and adjustment roll spacing is that 0.2mm starts thin logical and beats triangle bag 6 times, adjustment roll spacing
For bottom sheet after 1.6mm, after placing 12h naturally, 5g rubber compound is taken to measure technique sulfurizing time t at 150 DEG C on vulcameter90,
Then (curing temperature is 150 DEG C, sulfide stress 10MPa, vulcanization time t for vulcanization on vulcanizing press90), with cut-off knife point
Tensile sample and tearing sample are not determined.Heat-resistant air aging property is tested by GB/T3512-2001 standard, aging temperature
Be 100 DEG C, the time be respectively for 24 hours, 48h.The mechanical property parameters of rubber composite material are as shown in table 3 before and after aging.
The mechanical property of rubber composite material before and after 3 aging of table
3-0: unaged；3-1: aging is for 24 hours；3-2: aging 48h
Pass through the mechanical property of rubber composite material before and after contrast table 1, table 2,3 aging of table, it can be seen that natural astaxanthin
And its esters are carried on after filler after being added to rubber composite material, the ageing-resistant performance of rubber composite material significantly improves, and says
It is a kind of environmentally protective efficient anti-aging method for rubber composite material that bright natural astaxanthin and its esters, which are carried on filler,.
Basic principle of the invention is as follows:
Natural astaxanthin is a kind of keto-acid carotenoid of non-vitamin A original.Natural astaxanthin molecule is by 4 isoamyls
Diene double bonds head and the tail are formed by connecting, and share 11 conjugated double bonds, and conjugated double bond chain end there are also unsaturated ketone group and
Hydroxyl, wherein hydroxyl and ketone group constitute alpha-alcohol ketone again, this design feature makes it have more active electronic effect, can be to certainly
Electronics is provided by base or attracts the unpaired electron of free radical, to remove free radical.Natural astaxanthin and its esters are being had
It is dissolved in solvent, adds gum filler and stir and dry to constant weight, be finally added to that rubber is made in rubber
Composite material, wherein natural astaxanthin and its esters account for the 0.1%~10% of packing quality score.Natural astaxanthin and its esters
Be carried on filler as free radical scavenger, be then added in rubber composite material, improve rubber composite material thermal stability,
The ageing properties such as photostability, thermo-oxidative stability, photooxidation stability, delay the aging of rubber composite material, extend its processing, storage
Service life during depositing and in product use process, and due to being carried on filler, dispersibility is more preferable, compared to direct mechanical blending
Formula addition has better anti-aging effect.
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
It also should be regarded as protection scope of the present invention with retouching.
Claims (10)
1. a kind of method that natural astaxanthin and its esters are carried on filler proof rubber composite material aging, it is characterised in that:
Natural astaxanthin and its esters are dissolved in organic solvent first, gum filler is added and stirs and be dried under vacuum to
Constant weight is finally added to that rubber composite material is made in rubber, and wherein natural astaxanthin and its esters account for packing quality score
0.1%~10%.
2. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber composite material aging
Method, it is characterised in that: the natural astaxanthin and its esters refers to a kind of non-dimension of the keto-acid for being widely present in organism
The carotenoid and its esters of raw element A original.
3. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber composite material aging
Method, it is characterised in that: the natural astaxanthin and its esters main source organism have shellfish (such as shrimps),
Algae (such as haematococcus pluvialis and fungi such as phaffia rhodozyma).
4. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber composite material aging
Method, it is characterised in that: the rubber be natural rubber and synthetic rubber.
5. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber composite material aging
Method, it is characterised in that: the filler of the rubber composite material can be divided into reinforcing agent and filler from reinforcing effect.
6. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber composite material aging
Method, it is characterised in that: the filler of the rubber composite material can by sources be divided into organic filler and inorganic filler.
7. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber composite material aging
Method, it is characterised in that: the filler of the rubber composite material can be divided into granular, fibrous, resin-like and piece by shape
Shape.
8. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber composite material aging
Method, it is characterised in that: natural astaxanthin and its esters are dissolved in organic solvent first, gum filler is added and sufficiently stirs
It mixes uniformly and is dried under vacuum to constant weight.
Specifically comprise the following steps:
(1) it weighs: weighing the natural astaxanthin for accounting for packing quality score 0.1%~10% and its esters are added in beaker；Claim
The reinforcing filler that amount accounts for rubber composite material total mass fraction 1%~80% is added in three-necked flask；
(2) it dissolves: the common organic solvents of 10ml~1000ml is added to ultrasonic dissolution natural astaxanthin and its ester in beaker
Class, duration 10-30min；
(3) it mixes: will be added in three-necked flask dissolved with the organic solvent of natural astaxanthin and its esters；
(4) it stirs: atmospheric agitation 0.5h~2h within the scope of 0 DEG C~80 DEG C；
(5) dry: aeration-drying is to constant weight within the scope of 10 DEG C~30 DEG C.
9. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber composite material aging
Method, it is characterised in that: the preparation method of the rubber composite material can include but is not limited to following steps:
(1) natural astaxanthin and its esters that are completely dried described in right 8 mixing: are added to mixer together with filler
In, control mixing initial temperature is 70~90 DEG C, is kneaded 8~10min, 130~160 DEG C of dump temperature, makes sizing material and filler material
Tentatively mixed；
(2) mill: the sizing material after mixing is subjected to mill on a mill, sulfur sulfide system or non-sulfur sulfide system is added
It is thin to lead to 6 times and beat bottom sheet after triangle bag as the crosslinking agent of the vulcanization of rubber, obtain rubber compound；
(3)t90Measurement: the rubber compound of 5g or so under cutting out on rubber compound is placed on vulcameter, measures the technique sulfuric of rubber compound
Change time t90；
(4) vulcanization sizing: different rubber compound samples are vulcanized under certain temperature and pressure, obtain vulcanizate.
10. a kind of natural astaxanthin according to claim 1 and its esters are carried on filler proof rubber material aging
Method, it is characterised in that: the vulcanizate sample puts hot air aging case into, 100 DEG C of constant temperature, aging for 24 hours, 48h.
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| CN110240758A (en) * | 2019-06-18 | 2019-09-17 | 宁国市正道橡塑零部件有限公司 | A kind of self-lubricating abrasion-resistant rubber material and preparation method thereof |
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| CN105670040A (en) * | 2016-02-25 | 2016-06-15 | 华南理工大学 | Loaded rubber anti-aging agent and preparation method and application thereof |
| CN108034089A (en) * | 2017-12-27 | 2018-05-15 | 青岛科技大学 | A kind of method that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters |
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| CN103396592A (en) * | 2013-07-11 | 2013-11-20 | 华南理工大学 | Supported rubber anti-aging agent, as well as preparation method and application thereof |
| CN104877178A (en) * | 2015-03-24 | 2015-09-02 | 北京化工大学 | Method for preparing aging-resistance rubber by utilization of halloysite slow-release anti-aging agent |
| CN105670040A (en) * | 2016-02-25 | 2016-06-15 | 华南理工大学 | Loaded rubber anti-aging agent and preparation method and application thereof |
| CN108034089A (en) * | 2017-12-27 | 2018-05-15 | 青岛科技大学 | A kind of method that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters |
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| CN110240758A (en) * | 2019-06-18 | 2019-09-17 | 宁国市正道橡塑零部件有限公司 | A kind of self-lubricating abrasion-resistant rubber material and preparation method thereof |
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