CN108034089A - A kind of method that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters - Google Patents
A kind of method that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters Download PDFInfo
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- CN108034089A CN108034089A CN201711449478.2A CN201711449478A CN108034089A CN 108034089 A CN108034089 A CN 108034089A CN 201711449478 A CN201711449478 A CN 201711449478A CN 108034089 A CN108034089 A CN 108034089A
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- composite material
- rubber composite
- esters
- natural astaxanthin
- rubber
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- 239000005060 rubber Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 235000013793 astaxanthin Nutrition 0.000 title claims abstract description 67
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 title claims abstract description 65
- 239000001168 astaxanthin Substances 0.000 title claims abstract description 65
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 title claims abstract description 65
- 229940022405 astaxanthin Drugs 0.000 title claims abstract description 65
- 150000002148 esters Chemical class 0.000 title claims abstract description 45
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- 238000000034 method Methods 0.000 title claims abstract description 37
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- FMKGDHLSXFDSOU-BDPUVYQTSA-N Dienon-Astacin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)C(=O)C(=CC1(C)C)O)C=CC=C(/C)C=CC2=C(C)C(=O)C(=CC2(C)C)O FMKGDHLSXFDSOU-BDPUVYQTSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
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- 241001417495 Serranidae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 206010042496 Sunburn Diseases 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- JKQXZKUSFCKOGQ-LQFQNGICSA-N Z-zeaxanthin Natural products C([C@H](O)CC=1C)C(C)(C)C=1C=CC(C)=CC=CC(C)=CC=CC=C(C)C=CC=C(C)C=CC1=C(C)C[C@@H](O)CC1(C)C JKQXZKUSFCKOGQ-LQFQNGICSA-N 0.000 description 1
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- 230000001093 anti-cancer Effects 0.000 description 1
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- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 description 1
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- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 description 1
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- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of method that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters is invented, natural astaxanthin and its esters are added directly into rubber composite material as free radical scavenger, wherein the mass fraction of natural astaxanthin and its esters in rubber composite material is 0.05%~5%.Natural astaxanthin and its esters are added in rubber composite material as free radical scavenger, can improve the ageing properties such as the heat endurance of rubber composite material, thermo-oxidative stability, photostability, photooxidation stability, extend the service life of rubber composite material.Natural astaxanthin and its esters have many advantages, such as green natural, derive from a wealth of sources, is efficient, is nontoxic, and when use need to be only mixed into rubber composite material by conventional process tools, easy and effective without special process, method.The present invention opens a new field for the application of natural astaxanthin and its esters, and the also anti-aging for rubber composite material proposes new material and method.
Description
Technical field
The present invention relates to the preparation method of rubber composite material, more particularly, to one kind natural astaxanthin and its esters system
The method of standby ageing-resistant rubber composite material.
Background technology
Rubber composite material is due to combining the high resiliency of rubber, good insulating properties and the high-modulus of reinforcement and filler material
With designability it is strong the advantages that, thus be widely used in the every field such as industry, agricultural, building, traffic, life.But phase
For other traditional materials such as ceramic material and metal material, the performance of rubber composite material is being processed, storing or used
Cheng Zhong, is easily influenced and effect by external environmental factor, performance occurs and gradually degenerate, or even loses use value, i.e. rubber is old
Change.Thus preparing ageing-resistant rubber composite material has important practical significance.
Rubber and the occurrence and development of rubber aging, be one from outward appearance to inner essence, by the process of quantitative change to qualitative change.Aging
The change occurred in appearance afterwards is that surface spot occurs, tarnish or has micro-crack etc., and feel is softening stickness or is hardened
Embrittlement；Aging deteriorates some physical and chemical performances and electric property of rubber, and various mechanical properties occur different degrees of
Decline, ageing time it is longer change it is more notable.
Cause the principal element of rubber composite material aging 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 its molecule, the bond energy of cross-linked network and macromolecular
Cohesive energy easily by various erosions, is destroyed and aging all than relatively low.External factor can be divided into three classes, first, physical factor, as light,
Heat, electricity, high-energy radiation and mechanical stress etc.；Second, chemical factor, as oxygen, ozone, strong oxidizer, inorganic acid, alkali, salt it is water-soluble
Liquid and variable valency metal ions etc.；Third, biological factor, such as microorganism and ant.The oxidation of rubber and ozonization are to rubber
Destruction is most commonly seen caused by glue, also most serious.In addition the factor such as heat, light, mechanical stress toward contact to aoxidizing and having ozonized
To activation and/or catalytic action.Biological aging mostly occurs in the torrid zone or subtropical zone.Research shows that rubber composite material exists
Aging is an autocatalysis process under light, heat and oxygen or collective effect, is mainly carried out according to radical reaction course.
For the principal element and agine mechaism for causing rubber composite material aging, in rubber industry many methods by with
To improve the ageing-resistant performance of rubber composite material.At present, main the having of method of rubber composite material anti-aging property is improved
Method and Physical, chemical method are mainly the chemical constitution by improving copolymer, introduce the structure containing stable group, such as adopt
Modification by copolymerization is carried out with the vinyl groups containing antioxidant to improve the anti ageing property of rubber composite material；Physical laws master
If by adding the additives of various raising ageing-resistant performances, such as antioxidant and light stabilizer, or in rubber composite wood
Face coat etc. is expected to improve the ageing-resistant performance of rubber composite material.It is that rubber is compound wherein to add antioxidant and light stabilizer
Most general in material, most convenient and most economical method, but the antioxidant of these traditional rubber composite materials often has
Certain toxicity, has large effect to environment, especially for the rubber composite material of food-grade, therefore seeks efficiently low
The rubber composite material antioxidant of poison is always the major issue of rubber industry.
Natural astaxanthin, also known as astacin, are a kind of ketone group containing carotenoid, are widely present in the algaes such as haematococcus pluvialis
In the aquatic animals such as class and shrimp, crab and salmon.Early in the 1930s, researcher just isolates this spy from the shell of shrimp crab
Different keto-acid carotenoid, in the 1980s, astaxanthin with its remarkable antioxidation activity and strengthen immunity, anticancer
Antitumor isoreactivity function causes the extensive concern of people.
Natural astaxanthin resource is limited, and most of business astaxanthin is all artificial synthesized, and astaxanthin is carotenoid
The highest level product of synthesis, therefore, in common carotenoid, the antioxidation activity of astaxanthin is most strong, natural shrimp
The oxidation resistance of blue or green element is far above other bioactive substances, such as its radical scavenging activity is 500 times of vitamin E
More than, it is more than ten times of other carotenoid such as beta carotene and zeaxanthin.In nature, astaxanthin is by algae
Produced Deng photosynthesis of plant, the positions such as head capsule and body are stored in after shrimp crab etc. is edible, therefore, astaxanthin also has good
Pigmentation.At present, astaxanthin is as excellent antioxidant and colouring agent, be mainly used in pharmacy, cosmetics, food,
In drink, health products and aquaculture, have a good application prospect.Such as in pharmaceutical field, publication number CN104644698A
Disclose a kind of product for preventing senile dementia and preparation method thereof；Publication number CN105664042A discloses one kind and treats constipation
Chinese medicinal preparation method；Publication number CN101313897 provides microbial source phaffia rhodozyma astaxanthin and is preparing II type that prevents
Purposes in the medicine of diabetes.In cosmetic field, US6433025, which discloses natural astaxanthin, to be slowed down or is preventing ultraviolet
Application in terms of sunburn.In food service industry, publication number CN105901165A provides a kind of sesame oil rich in natural astaxanthin
And preparation method thereof；Publication number CN105767586A is related to a kind of fortification egg feed and its application of poultry farming；It is public
The number of opening CN102125093A discloses dairy products of astaxanthin-containing and preparation method thereof.In field of beverage, publication number
CN105029570A discloses a kind of astaxanthin health drink with function of delaying senility；Publication number CN104893932A is disclosed
A kind of oceanic functional with effect of lowering blood sugar compound assembled alcoholic drinks；Publication number CN103783614A discloses a kind of astaxanthin
Apple vinegar beverage.In health products trade, publication number CN104187668A provide it is a kind of with healthcare function, people can be improved
The nutrient and healthcare products containing natural astaxanthin of body oxidation resistance；Publication number CN101053409 provides a kind of blue or green with natural shrimp
Vegetable oil, edible fats, natural are raw material, and capsule or piece containing natural astaxanthin are made of common process
Agent；Publication number CN105031314A discloses a kind of marine health capsule with effect of regulating blood fat.In aquaculture field,
Publication number CN105831494A is related to a kind of cultivation mixed fodder for strengthening salmon trophic function and color and luster；Publication number
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CN101999544A provides a kind of aquaculture composite bait rich in astaxanthin and preparation method thereof.
So far, the answering in rubber composite material anti-aging field without document report natural astaxanthin and its esters
With.Natural astaxanthin and its esters are a kind of natural materials extracted out of animal and plant body, environment-protecting and non-poisonous, will not be compound to rubber
Material and environment have harmful effect.
The content of the invention
For rubber composite material antioxidant toxicity in background technology it is larger, not environmentally the problem of, the purpose of the present invention exists
In a kind of safe and environment-friendly method that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters of offer.
Rubber composite material aging under light, heat and oxygen or its collective effect is an autocatalysis process, is mainly pressed
Carried out according to radical reaction course, and natural astaxanthin and its phenolic hydroxyl structure of esters uniqueness 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 scattered in rubber composite material matrix, and the characteristics of efficiently catching free radical using natural astaxanthin and its esters can be with
The effective free radical for catching elastomeric material and being produced under light, heat and oxygen or its collective effect, so as to effectively delay rubber
The ageing process of glue composite material.
The present invention solves the technical solution that technical problem uses：
Natural astaxanthin and its esters are added in rubber composite material as free radical scavenger, natural astaxanthin and
Mass fraction of its esters in rubber composite material is 0.05%~5%.
The natural astaxanthin, scientific name 3,3'- dihydroxy -4,4'- diketos-β, β '-carrotene, molecular formula are
C40H52O4, relative molecular weight 596.86 is a kind of keto-acid carotenoid of non-vitamin A originals, 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 and form, share 11 conjugated double bonds, and also have undersaturated ketone group and hydroxyl in conjugated double bond chain end, wherein hydroxyl and
Ketone group forms alpha-alcohol ketone again, this design feature makes it have more active electronic effect, can to free radical provide electronics or
Attract the unpaired electron of free radical, so as to remove free radical.
The natural astaxanthin and its main source organism of esters have：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 strengthening action.
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.
Natural astaxanthin and its esters are improved its ageing-resistant performance by the present invention applied to rubber composite material, have with
Lower feature：
(1) antioxidant of traditional rubber composite material is typically from chemical synthesis, often with certain toxicity, no matter
From production still 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
Ring, the anti-aging of this rubber composite material to rubber composite material particularly food-grade is of great significance.
(2) natural astaxanthin and its esters are added to rubber composite material by the present invention as free radical scavenger, are improved
The ageing properties such as the heat endurance of rubber composite material, thermo-oxidative stability, photostability, photooxidation stability, it is compound to extend rubber
The service life of material.It need to be only mixed into during use by conventional process tools in rubber composite material, at special technique
Reason, method are easy and effective.
(3) due to its own unique physicochemical properties, it is answered in efficiently improvement rubber for natural astaxanthin and its esters
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 to be present in a kind of renewable, sustainable use natural resources of nature, this
The application and development invented as natural astaxanthin and its esters opens a new application field, is also the anti-of rubber composite material
Aging proposes new material and method.
Embodiment
With reference to embodiment and subordinate list, the invention will be further described.
Embodiment 1：194.3g natural rubbers (SMR10) after plasticating are added in mixer, and setting rotating speed is
70rpm, initial temperature are 90 DEG C, start to be kneaded, and 97.15g white carbons and the mixture of 7.77gSi-69 are added after 2min, are kneaded
9.72g stearic acid, 3.89g zinc oxide, the mixture of 2.92g accelerator NSs are 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 rotating speed is 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 bag roller, add after 4.27g Sulfurs 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 bottom sheet after 1.6mm, after placing 12h naturally, takes 5g rubber compounds in sulphur
Change and measure technique sulfurizing time t on instrument at 150 DEG C90, then (curing temperature is 150 DEG C, vulcanization for vulcanization on vulcanizing press
Pressure is 10MPa, vulcanization time t90), determine tensile sample and tear sample respectively with cut-off knife.Heat-resistant air aging property is pressed
GB/T3512-2001 standards are tested, and aging temperature is 100 DEG C, and the time is respectively 24h, 48h.Rubber is compound before and after aging
The mechanical property of material is 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 24h；1-2：Aging 48h
Embodiment 2：193.7g natural rubbers (SMR10) after plasticating are added in mixer, and setting rotating speed is
70rpm, initial temperature are 90 DEG C, start to be kneaded, added after 2min 96.85g white carbons, 0.97g natural astaxanthins and
The mixture of 7.75gSi-69, is kneaded the mixing of addition 9.69g stearic acid, 3.87g zinc oxide, 2.91g accelerator NSs after 4min
Thing, stops mixing, 140 DEG C of sizing material temperature after being kneaded 2min；Sizing material is put while hot on a mill, setting rotating speed is 15rpm, preceding
55 DEG C of roller, 50 DEG C of back roller, roller speed is than being 1:1.1, roll spacing 1mm, 3 knives are respectively cut in left and right after bag roller, add left again after 4.26g Sulfurs
3 knives are respectively cut on the right side, and adjustment roll spacing starts thin logical and beats triangle bag 6 times for 0.2mm, and adjustment roll spacing is bottom sheet after 1.6mm, is placed naturally
After 12h, 5g rubber compounds are taken to measure technique sulfurizing time t at 150 DEG C on vulcameter90, then vulcanize on vulcanizing press
(curing temperature is 150 DEG C, sulfide stress 10MPa, vulcanization time t90), determine tensile sample respectively with cut-off knife and tear tries
Sample.Heat-resistant air aging property is tested by GB/T3512-2001 standards, aging temperature be 100 DEG C, the time be respectively 24h,
48h.The mechanical property of rubber composite material is 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：It is unaged；2-1：Aging 24h；2-2：Aging 48h
Embodiment 3：193.1g natural rubbers (SMR10) after plasticating are added in mixer, and setting rotating speed is
70rpm, initial temperature are 90 DEG C, start to be kneaded, added after 2min 96.55g white carbons, 1.93g natural astaxanthins and
The mixture of 7.72gSi-69, is kneaded the mixing of addition 9.66g stearic acid, 3.86g zinc oxide, 2.90g accelerator NSs after 4min
Thing, stops mixing, 141 DEG C of sizing material temperature after being kneaded 2min；Sizing material is put while hot on a mill, setting rotating speed is 15rpm, preceding
55 DEG C of roller, 50 DEG C of back roller, roller speed is than being 1:1.1, roll spacing 1mm, 3 knives are respectively cut in left and right after bag roller, add left again after 4.25g Sulfurs
3 knives are respectively cut on the right side, and adjustment roll spacing starts thin logical and beats triangle bag 6 times for 0.2mm, and adjustment roll spacing is bottom sheet after 1.6mm, is placed naturally
After 12h, 5g rubber compounds are taken to measure technique sulfurizing time t at 150 DEG C on vulcameter90, then vulcanize on vulcanizing press
(curing temperature is 150 DEG C, sulfide stress 10MPa, vulcanization time t90), determine tensile sample respectively with cut-off knife and tear tries
Sample.Heat-resistant air aging property is tested by GB/T3512-2001 standards, aging temperature be 100 DEG C, the time be respectively 24h,
48h.The mechanical property of rubber composite material is 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：It is unaged；3-1：Aging 24h；3-2：Aging 48h
Pass through the mechanical property before and after contrast table 1, table 2,3 rubber composite material aging of table, it can be seen that compound in rubber
After adding natural astaxanthin and its esters in material, the ageing-resistant performance of rubber composite material significantly improves, and illustrates that natural shrimp is blue or green
Element and its esters are a kind of environmentally protective efficient antioxidants for rubber composite material.
The basic principle of the present invention is as follows：
Natural astaxanthin, is a kind of keto-acid carotenoid of non-vitamin A originals.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 also have undersaturated ketone group and
Hydroxyl, wherein hydroxyl and ketone group form 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, so as to remove free radical.Using natural astaxanthin and its esters as
Free radical scavenger is added in rubber composite material, the mass fraction of natural astaxanthin and its esters in rubber composite material
For 0.05%~5%.Natural astaxanthin and its esters are added in rubber composite material as free radical scavenger, improve rubber
The ageing properties such as the heat endurance of composite material, thermo-oxidative stability, photostability, photooxidation stability, extend rubber composite material
Service life.
The above is not limitation of the present invention, it should be pointed out that：Come for those skilled in the art
Say, on the premise of essential scope of the present invention is not departed from, some 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 (9)
- A kind of 1. method that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters, it is characterised in that：Will be natural Astaxanthin and its esters are added directly into rubber composite material as free radical scavenger, wherein natural astaxanthin and its esters Mass fraction in rubber composite material is 0.05%~5%.
- A kind of 2. side that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters according to claim 1 Method, it is characterised in that：The natural astaxanthin and its esters refers to a kind of keto-acid non-vitamin A for being widely present in organism Former carotenoid and its esters.
- 3. a kind of method that resistance to old rubber composite material is prepared with natural astaxanthin and its esters according to claim 1, It is characterized in that：The natural astaxanthin and its esters main source organism has shellfish (such as shrimps), algae (such as Haematococcus pluvialis and fungi such as phaffia rhodozyma).
- A kind of 4. side that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters according to claim 1 Method, it is characterised in that：The rubber is natural rubber and synthetic rubber.
- A kind of 5. side that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters according to claim 1 Method, it is characterised in that：The filler of the rubber composite material can be divided into reinforcing agent and filler from strengthening action.
- A kind of 6. side that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters according to claim 1 Method, it is characterised in that：The filler of the rubber composite material can by sources be divided into organic filler and inorganic filler.
- A kind of 7. side that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters according to claim 1 Method, it is characterised in that：The filler of the rubber composite material can be divided into granular, fibrous, resin-like and sheet by shape.
- A kind of 8. side that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters according to claim 1 Method, it is characterised in that：The preparation method of the rubber composite material, can include but is not limited to following steps：(1) mixing：By natural astaxanthin and its esters according to rubber composite material mass fraction 0.05%~5% with filler one Rise and be added in mixer, it is 70~90 DEG C to control mixing initial temperature, 8~10min of mixing, 130~160 DEG C of dump temperature, Sizing material is set tentatively to be mixed with filler；(2) mill：Sizing material after mixing is subjected to mill on a mill, adds sulfur sulfide system or non-sulfur vulcanization body It is the crosslinking agent as the vulcanization of rubber, it is thin to lead to 6 times and beat bottom sheet after triangle bag, obtain rubber compound；(3)t90Measure：The rubber compound of 5g or so, is placed on vulcameter, measures the technique sulfuric of rubber compound under being cut out on rubber compound Change time t90；(4) vulcanization sizing：Different rubber compound samples are vulcanized under certain temperature and pressure, obtain vulcanizate.
- A kind of 9. side that ageing-resistant rubber composite material is prepared with natural astaxanthin and its esters according to claim 1 Method, it is characterised in that：The vulcanizate sample puts hot air aging case, 100 DEG C of constant temperature, aging 24h, 48h into.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320774A (en) * | 2018-10-16 | 2019-02-12 | 青岛科技大学 | A kind of method that natural astaxanthin and its esters are carried on filler proof rubber composite material aging |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153779A (en) * | 2011-03-04 | 2011-08-17 | 浙江理工大学 | Anti-aging method for polymer materials |
| CN106318878A (en) * | 2015-07-06 | 2017-01-11 | 中国科学院青岛生物能源与过程研究所 | Red yeast engineering bacterium for high-yield production of astaxanthin and construction method thereof |
| CN107163413A (en) * | 2017-06-02 | 2017-09-15 | 浙江龙圣华橡胶有限公司 | A kind of conveyer belt and its manufacture method |
-
2017
- 2017-12-27 CN CN201711449478.2A patent/CN108034089A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153779A (en) * | 2011-03-04 | 2011-08-17 | 浙江理工大学 | Anti-aging method for polymer materials |
| CN106318878A (en) * | 2015-07-06 | 2017-01-11 | 中国科学院青岛生物能源与过程研究所 | Red yeast engineering bacterium for high-yield production of astaxanthin and construction method thereof |
| CN107163413A (en) * | 2017-06-02 | 2017-09-15 | 浙江龙圣华橡胶有限公司 | A kind of conveyer belt and its manufacture method |
Non-Patent Citations (4)
| Title |
|---|
| 丁绍兰: "《革制品材料学》", 30 September 2001, 中国轻工业出版社 * |
| 杨清芝: "《现代橡胶工艺学》", 30 June 1997, 中国石化出版社 * |
| 王明荣灯: "《中华医学百科全书》", 31 January 2017, 中国协和医科大学出版社 * |
| 肖素荣等: "虾青素生产方法研究进展", 《中国食物与营养》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320774A (en) * | 2018-10-16 | 2019-02-12 | 青岛科技大学 | A kind of method that natural astaxanthin and its esters are carried on filler proof rubber composite material aging |
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