CN106084321A - A kind of ageing-resistant natural rubber and preparation method thereof - Google Patents
A kind of ageing-resistant natural rubber and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of ageing-resistant natural rubber and preparation method thereof, the preparation method of this ageing-resistant natural rubber includes: add modified rare earth carboxylate dispersion in natural rubber latex Ruzhong, then wood vinegar is used as coagulator, natural rubber latex to be solidified, creped obtain film, after film is at room temperature hung a period of time, employing hot air drier is dried, and obtains ageing-resistant natural rubber.The natural rubber that the present invention prepares has ageing-resistant performance, low thermogenesis performance and the good anti-microbial property of excellence, may be used for the natural rubber products such as tire, sebific duct, medical latex product, sole.The method technique of the present invention is simple, constant product quality, it is easy to industrialized production.
Description
Technical field
The present invention relates to the technical field of a kind of natural rubber, particularly to a kind of ageing-resistant natural rubber and preparation side thereof
Method.
Background technology
Natural rubber is a kind of with the suitable Isosorbide-5-Nitrae-polyisoprene natural polymer as main component, at normal temperatures
Having higher elasticity, slightly band plasticity, mechanical strength is high and electrical insulation capability is good, is the most most widely used general purpose rubber.
Containing unsaturated double-bond in the structure of natural rubber, it is the material that a kind of chemical reaction ability is stronger, light, heat, smelly
Oxygen, radiate, subdue deformation and the metal such as copper, manganese can make the original chemical constitution of destruction rubber, and then cause natural rubber products
In processing or be susceptible to during using aging, the most ageing-resistant is the deadly defect of natural rubber, and natural rubber products is universal
Have that period of storage is short, service life is short, the aging problem such as tacky.At present, the aging preventive means of natural rubber is mainly
Add amine and phenols antiaging agent, but this kind of antiaging agent can bring ill effect simultaneously, as phenols antiaging agent protects
Performance is weak, and amine antiaging agent the most easily makes rubber variable color or surface bloom occur, produce some carcinogen, and to sky
So the aging protection effect of rubber is undesirable.
Summary of the invention
In view of this, present invention aim at natural rubber that a kind of ageing-resistant performance excellence is provided and preparation method thereof,
While improving natural rubber ageing-resistant performance, improve the antibiotic property of natural rubber, reduce the thermogenesis performance of natural rubber.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme:
The invention provides a kind of ageing-resistant natural rubber, including the component of following weight portion:
Dry glue meter natural rubber latex 100 parts, rare earth carboxylate 0.01～10 parts, surfactant 0.05～0.2 part, even
Connection agent 0.02～4 parts, coagulator 20～80 parts；
Preferably rare earth carboxylate is that oleic acid rare earth, rare-earth stearate, lauric acid rare earth, malic acid rare earth, citric acid are dilute
Any one or more mixture in soil, rare earth palmitate and salicylic acid rare earth；
Preferably the rare earth element in rare earth carboxylate be lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,
Any one in ytterbium, lutecium, scandium and yttrium；
Preferably surfactant is dodecyl sodium sulfate, sodium lauryl sulphate, sodium lignin sulfonate and lignin
Any one or a few in sulfoacid calcium；
Preferably coupling agent is 3-aminopropyl triethoxysilane (KH550), 3-glycydoxy trimethoxy
Base silane (KH560), 3-(methacryloxypropyl) propyl trimethoxy silicane (KH570) and double-(γ-triethoxysilylpropyl)
In tetrasulfide (Si69) any one or a few；
Preferably coagulator is wood vinegar, and the pH value of preferred wood vinegar is 3.0～4.2；
Preferably the mass content of natural rubber latex Ruzhong nitrogen is 0.01～0.52%；
The invention provides the preparation method of a kind of ageing-resistant natural rubber, comprise the steps:
(1) under ultrasound condition, rare earth carboxylate, surfactant and coupling agent are reacted in aqueous phase system, obtains
Modified RE carboxylate dispersion；
(2) described modified RE carboxylate dispersion is mixed with natural rubber latex, continue ultrasonic, obtain latex state
Ageing-resistant natural rubber；
(3) the ageing-resistant natural rubber of described latex state is mixed with coagulator, after solidification, obtain ageing-resistant natural rubber
Glue；
Also including being dried after preferred described solidification, the mode being dried is: by the product after described solidification in natural conditions
Under be dried 1～30 day, under the conditions of 40～80 DEG C, be then dried 2～48h.
The invention provides sizing material prepared by a kind of ageing-resistant natural rubber utilizing such scheme to obtain, including following weight
The component of amount part: the ageing-resistant natural rubber of dry glue meter 100 parts, zinc oxide 4～6 parts, stearic acid 1～3 parts, the N-tert-butyl group-2-benzene
And the yellow amide (accelerator NS) of thiazole time 0.5～1 part, sulfur 2～2.5 parts, white carbon black 30～40 parts.
The invention provides a kind of ageing-resistant natural rubber, it is mainly composed of: dry glue meter natural rubber latex 100 parts,
Rare earth carboxylate 0.01～10 parts, surfactant 0.05～0.2 part, coupling agent 0.02～4 parts, coagulator 20～80 parts.This
Invention utilize surfactant and coupling agent that rare earth carboxylate is modified, utilize modified rare earth carboxylate catch grab natural
The free radical that ageing of rubber process produces, improves the ageing-resistant performance of natural rubber；Improve the crosslink density of natural rubber simultaneously,
Thus further increase the ageing-resistant performance of natural rubber, reduce the thermogenesis performance of natural rubber.
The ageing-resistant natural rubber preparation method that the present invention provides does not affects processing characteristics and the physical and mechanical properties of sizing material,
And preparation method is simple, with low cost, it is easy to large-scale production.
Detailed description of the invention
The invention provides a kind of ageing-resistant natural rubber, including the component of following weight portion:
Dry glue meter natural rubber latex 100 parts, rare earth carboxylate 0.01～10 parts, surfactant 0.05～0.2 part,
Coupling agent 0.02～4 parts, coagulator 20～80 parts.
The ageing-resistant natural rubber that the present invention provides is with natural rubber latex as matrix, with the weight of described natural rubber latex
On the basis of amount number, weight by dry rubber, it is set as 100 parts.In the present invention, the mass content of described natural rubber latex Ruzhong nitrogen is excellent
Elect 0.01～0.52% as, more preferably 0.12～0.43%, most preferably 0.2～0.4%；Consolidating of described natural rubber latex
Content is preferably 20%～40%, more preferably 25%～35%.
The ageing-resistant natural rubber that the present invention provides includes the rare earth carboxylate of 0.01～10 weight portions, preferably 0.1～8
Part, more preferably 1～6 part, most preferably 2～5 parts.In the present invention, described rare earth carboxylate is preferably oleic acid rare earth, tristearin
In acid rare earth, lauric acid rare earth, malic acid rare earth, citric acid rare earth, rare earth palmitate and salicylic acid rare earth any one or
Multiple mixture；Rare earth element in described rare earth carboxylate be preferably for lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium,
Any one in holmium, erbium, thulium, ytterbium, lutecium, scandium and yttrium；Described rare earth carboxylate is preferably malic acid neodymium, malic acid cerium, Petiolus Trachycarpi
Acid lanthanum, stearic acid neodymium, Lanthanum salicylate, lauric acid praseodymium and oleic acid lanthanum；More preferably malic acid neodymium, Palmic acid lanthanum, stearic acid neodymium and
Lanthanum salicylate；
The free radical that the present invention utilizes rare earth carboxylate to produce in natural rubber oxidizing process is combined, and makes oxidation reaction eventually
Only, thus restrained effectively proceeding of Oxidation, improve the ageing-resistant performance of natural rubber.
The ageing-resistant natural rubber that the present invention provides includes the surfactant of 0.05～0.2 weight portion, preferably 0.1～
0.15 part, more preferably 0.12 part.In the present invention, described surfactant is preferably anion surfactant, more preferably
For any one or a few in dodecyl sodium sulfate, sodium lauryl sulphate, sodium lignin sulfonate and calcium lignosulfonate.
The ageing-resistant natural rubber that the present invention provides includes the coupling agent of 0.02～4 weight portions, preferably 0.05～0.35
Part, more preferably 0.1～0.25 part.In the present invention, described coupling agent is preferably silane coupler, more preferably 3-aminopropyl
Triethoxysilane, 3-glycydoxy trimethoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicon
In alkane and double-(γ-triethoxysilylpropyl) tetrasulfide any one or a few.
The present invention uses surfactant and coupling agent to be modified rare earth carboxylate, utilizes surfactant to improve dilute
Soil carboxylate and high molecular affinity, make rare earth carboxylate be easier in nature rubber latex and be uniformly dispersed, improve rare earth
Carboxylate and the compatibility of nature rubber latex；Coupling agent is utilized to make rare earth carboxylate surface cover the upper and rubber molecule compatibility
Organo-functional group that is good and that can react with rubber molecule, improves the binding ability of rare earth carboxylate and natural rubber, thus
Enable the most modified rare earth carboxylate to be uniformly dispersed in nature rubber latex, more effectively catch and grab natural rubber
The free radical that ageing process produces, improves the ageing-resistant performance of natural rubber；Improve the crosslink density of natural rubber simultaneously, enter one
Step improves the ageing-resistant performance of natural rubber, reduces the thermogenesis performance of natural rubber.
The ageing-resistant natural rubber that the present invention provides includes the coagulator of 20～80 weight portions, preferably 30～70 parts, more
It is preferably 40～60 parts.In the present invention, described coagulator is preferably wood vinegar；The pH value of described wood vinegar be preferably 3.0～
4.2, more preferably 3.5～4.0.The present invention utilizes wood vinegar as the coagulator of natural rubber, improves the antibacterial of natural rubber
Property, it is to avoid biting of mosquito, thus improve the ageing-resistant performance of natural rubber；The wood vinegar that the present invention uses is vegetable raw material
The condensed recovery of admixture of gas produced in carbonization or retort process separates the organic products obtained, and main component is acetic acid,
Wide material sources, low cost.
The invention provides the preparation method of ageing-resistant natural rubber described in technique scheme, comprise the steps:
(1) under ultrasound condition, rare earth carboxylate, surfactant and coupling agent are reacted in aqueous phase system, obtains
Modified RE carboxylate dispersion；
(2) described modified RE carboxylate dispersion is mixed with natural rubber latex, continue ultrasonic, obtain latex state
Ageing-resistant natural rubber；
(3) the ageing-resistant natural rubber of described latex state is mixed with coagulator, after solidification, obtain ageing-resistant natural rubber
Glue.
Rare earth carboxylate, surfactant and coupling agent are reacted under ultrasound condition in aqueous phase system by the present invention,
To modified RE carboxylate dispersion.In the present invention, described ultrasonic power is preferably 750～1000W, more preferably 800
～950W；Described ultrasonic temperature is preferably 50～90 DEG C, more preferably 55～80 DEG C；The described ultrasonic time be preferably 1～
6h, more preferably 1.5～5h, most preferably 2～3.5h；In the present invention, the mode of heating of described ultrasonic procedure is preferably water
Bath heating.
The present invention carries out ultrasonic the most under agitation, and the speed of described stirring is preferably 200～400r/min, more excellent
Elect 250～350r/min as.In the present invention, the consumption of described rare earth carboxylate, surfactant and coupling agent and kind with
Described in technique scheme unanimously, do not repeat them here.
In the present invention, described aqueous phase system is preferably provided by deionized water, deionized water and dry glue meter natural rubber latex
The mass ratio of breast is preferably 0.15～0.3:1, more preferably 0.2:1.
After obtaining modified RE carboxylate dispersion, the present invention is by described modified RE carboxylate dispersion and natural rubber
Latex mixes, and continues ultrasonic, obtains the ageing-resistant natural rubber of latex state.Power that in the present invention, described continuation is ultrasonic,
Ultrasonic temperature, stir speed (S.S.) and mode of heating is identical with step (1)；Described continuation ultrasonic time be preferably 0.5～
8h, more preferably 1～7h, most preferably 2～6h.In the present invention, the mass content of described natural rubber latex Ruzhong nitrogen is preferred
It is 0.01～0.52%, more preferably 0.1～0.5%, most preferably 0.2～0.4%.
After obtaining the ageing-resistant natural rubber of latex state, the present invention is by the described ageing-resistant natural rubber of latex state and solidification
Agent mixes, and obtains ageing-resistant natural rubber after solidification.In the present invention, the time of described solidification is preferably 1～6h, more preferably
2～5h；Described coagulator is preferably wood vinegar, and pH value and the consumption of described wood vinegar are consistent with such scheme.
In the present invention, the step being dried the most also is included after the solidification of described latex state ageing-resistantization natural rubber；Institute
State dry mode to be preferably: be dried under field conditions (factors) by the product after described solidification 1～30 day, then at 40～80 DEG C of bars
2～48h it are dried under part.
The present invention preferably carries out being dried under natural conditions again by after the product creped one-tenth film after solidification, described film
It is preferably dimensioned to be: 600～800mm × 200～400mm × 900～1000mm, more preferably: 750mm × 350mm × 950mm；
The present invention is preferably 1～30 day drying time under field conditions (factors), more preferably 5～25 days, most preferably 10～20 days；This
Inventing the drying mode under preferred natural conditions is hang airing；The present invention, after natural drying completes, preferably carries out second
Stage is dried, and the temperature that described second stage is dried is preferably 40～80 DEG C, more preferably 50～70 DEG C, described second stage
It is preferably 2～48h drying time, more preferably 5～36h, most preferably 10～30h.The present invention is by entering under field conditions (factors)
Row is dried and makes the cross-linked network of natural rubber more perfect, improves the ageing-resistant performance of natural rubber.
The invention provides sizing material prepared by a kind of ageing-resistant natural rubber utilizing such scheme to obtain, preferably include as
The component of lower weight portion: the ageing-resistant natural rubber of dry glue meter 100 parts, zinc oxide 4～6 parts, stearic acid 1～3 parts, the N-tert-butyl group-
The yellow amide (accelerator NS) of 2-[4-morpholinodithio time 0.5～1 part, sulfur 2～2.5 parts, white carbon black 30～40 parts；More preferably: dry glue
Count ageing-resistant natural rubber 100 parts, zinc oxide 5 parts, stearic acid 2 parts, the yellow amide (accelerator of the N-tert-butyl group-2-[4-morpholinodithio time
NS) 0.7 part, 2.25 parts of sulfur, white carbon black 35 parts.
It is described in detail below in conjunction with ageing-resistant natural rubber that the present invention is provided by embodiment and preparation method thereof,
But they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Adding the Lanthanum Stearate of 0.01 part in the deionization of 20 parts, control ultrasonic power is 750W, at ultrasonic disperse
Under state, add the dodecyl sodium sulfate of 0.05 part and 0.02 part of Silane coupling agent KH550, be placed in the water-bath of 50 DEG C continuously
Stirring 1h, control stir speed (S.S.) is 200r/min, prepares modified rare earth carboxylate dispersion, standby；
Modification obtained above is added in the natural rubber latex (weight by dry rubber) that 100 parts of nitrogen mass content are 0.05%
Lanthanum Stearate dispersion, continue ultrasonic agitation 0.5h, obtain the ageing-resistant natural rubber of latex state；
20 parts of the wood vinegar that pH is 3.0 is added, by latex state in the ageing-resistant natural rubber of the latex state obtained
The solidification of ageing-resistant natural rubber, creped obtain a size of 750mm × 350mm × 950mm film, film at room temperature hung
1 day, in the hot air drier of 60 DEG C, then it is dried 16h, obtains ageing-resistant natural rubber.
The ageing-resistant Natural Rubber Products obtained is carried out mixed refining process by the present invention, and basic recipe is ageing-resistant natural rubber
(dry glue meter) 100 parts, zinc oxide 5 parts, stearic acid 2 parts, accelerator NS 0.7 part, 2.25 parts of sulfur, white carbon black 35 parts；Park 12h
Rear survey optimum sulfurating time T90, vulcanizing press is carried out vulcanize (145 DEG C × T of conditions of vulcanization90), obtain sizing material.
According to GB/T3512-2001 (vulcanite or thermoplastic elastomer hot-air accelerated ageing and heat resistant test), GB/
T7762-2003 (vulcanite or the thermoplastic elastomer static tensile test of resistance to ozone-induced cracking), GB/T16585-1996 (sulfuration rubber
Glue artificial weathering aging (fluorescent ultraviolet lamp) test method) to the resistance to air aging performance of gained sizing material, ozone-resistant aging property
It is measured with anti-ultraviolet ageing performance；
According to GB/T 1687-1993, (vulcanite is the mensuration of temperature rise and fatigue performance the 2nd in angular test
Point--compression angular test) thermogenesis performance of gained sizing material is tested；Test result is shown in Table 1.
Embodiment 2
Adding the cerium citrate of 1 part in the deionization of 25 parts, control ultrasonic power is 1000W, at the shape of ultrasonic disperse
Under state, add the sodium lignin sulfonate of 0.08 part and 0.06 part of silane coupler KH560, be placed in continuous stirring in the water-bath of 60 DEG C
4h, control stir speed (S.S.) is 400r/min, prepares modified rare earth carboxylate dispersion, standby；
Modification obtained above is added in the natural rubber latex (weight by dry rubber) that 100 parts of nitrogen mass content are 0.01%
Cerium citrate dispersion, continue ultrasonic agitation 8h, obtain the ageing-resistant natural rubber of latex state；
Adding pH in the ageing-resistant natural rubber of the latex state obtained is that 80 parts of the wood vinegar of 4.0 is by latex state
Ageing-resistant natural rubber solidifies, and creped obtains 750mm × 250mm × 900mm film, and film at room temperature hangs 3 days, then
In the hot air drier of 60 DEG C, it is dried 2h, obtains ageing-resistant natural rubber.
According to the method described in embodiment 1, ageing-resistant Natural Rubber Products is made sizing material, the performance of sizing material is surveyed
Examination, test result is shown in Table 1.
Embodiment 3
Adding the Palmic acid lanthanum of 2 parts in the deionization of 30 parts, control ultrasonic power is 800W, in the state of ultrasonic disperse
Under, add the calcium lignosulfonate of 0.2 part and 4 parts of silane coupler KH570, be placed in continuous stirring 6h in the water-bath of 90 DEG C, system
Obtain modified Palmic acid lanthanum dispersion, standby；
Modification obtained above is added in the natural rubber latex Ruzhong (weight by dry rubber) that 100 parts of nitrogen mass content are 0.09%
Palmic acid lanthanum dispersion, continue ultrasonic agitation 4h, obtain the ageing-resistant natural rubber of latex state；
Adding pH in the ageing-resistant natural rubber of the latex state obtained is that 40 parts of the wood vinegar of 3.5 is by latex state
Ageing-resistant natural rubber solidification, creped obtains a size of 700mm × 350mm × 900mm film, is at room temperature hung by film
7 days, in the hot air drier of 80 DEG C, then it is dried 24h, obtains ageing-resistant natural rubber.
According to the method described in embodiment 1, ageing-resistant Natural Rubber Products is made sizing material, the performance of sizing material is surveyed
Examination, test result is shown in Table 1.
Embodiment 4
Adding the Lanthanum salicylate of 1 part and the stearic acid neodymium of 3 parts in the deionization of 20 parts, control ultrasonic power is 850W,
When ultrasonic disperse, add the sodium lauryl sulphate of 0.1 part and 1 part of silane coupler Si69, be placed in the water of 80 DEG C
Continuous stirring 3h in bath, prepares modified rare earth carboxylate dispersion, standby；
Modification obtained above is added in the natural rubber latex (weight by dry rubber) that 100 parts of nitrogen mass content are 0.15%
Rare earth carboxylate dispersion, continues ultrasonic agitation 3h, obtains the ageing-resistant natural rubber of latex state；
Adding pH in the ageing-resistant natural rubber of the latex state obtained is that 50 parts of the wood vinegar of 4.2 is by latex state
Ageing-resistant natural rubber solidification, creped obtains a size of 750mm × 350mm × 950mm film, is at room temperature hung by film
30 days, in the hot air drier of 50 DEG C, then it is dried 3h, obtains ageing-resistant natural rubber.
According to the method described in embodiment 1, ageing-resistant Natural Rubber Products is made sizing material, the performance of sizing material is surveyed
Examination, test result is shown in Table 1.
Embodiment 5
In the deionization of 20 parts, add 0.5 part of malic acid lanthanum, the Lanthanum Stearate of 0.8 part, 3 parts of lauric acid lanthanums, control super
Acoustical power is 900W, when ultrasonic disperse, adds the dodecyl sodium sulfate of 0.2 part and 4 parts of silane couplers
KH550, is placed in continuous stirring 4h in the water-bath of 80 DEG C, prepares modified rare earth carboxylate dispersion, standby；
It is that 0.4% natural rubber latex Ruzhong adds modified rare earth carboxylate dispersion, stirring 100 parts of nitrogen mass content
8h, obtains the ageing-resistant natural rubber of latex state；
Adding pH in the ageing-resistant natural rubber of the latex state obtained is resistance to by latex state of 30 parts of 3.6 wood vinegar
Aging natural rubber solidification, the creped film obtaining a size of 750mm × 350mm × 950mm, at room temperature hangs film
20 days, in the hot air drier of 40 DEG C, then it is dried 2h, obtains ageing-resistant natural rubber.
According to the method described in embodiment 1, ageing-resistant Natural Rubber Products is made sizing material, the performance of sizing material is surveyed
Examination, test result is shown in Table 1.
Comparative example 1
Selecting 5# smoke sheet rubber to carry out mixed refining process, formula is 5# smoke sheet rubber 100 parts, zinc oxide 5 parts, stearic acid 2 parts, promotes
Agent NS 0.7 part, 2.25 parts of sulfur, white carbon black 35 parts.Survey optimum sulfurating time T90 after parking 12h, vulcanizing press is carried out
Sulfuration (145 DEG C × T90 of conditions of vulcanization).Test the performance of sizing material according to the method described in embodiment 1, test result is shown in Table 1.
Comparative example 2
Selecting 3L light color glue to carry out mixed refining process, formula is 100 parts of 3L light color glue, zinc oxide 5 parts, stearic acid 2 parts, promotes
Agent NS 0.7 part, 2.25 parts of sulfur, white carbon black 35 parts.Survey optimum sulfurating time T90 after parking 12h, vulcanizing press is carried out
Sulfuration (145 DEG C × T90 of conditions of vulcanization).Test the performance of sizing material according to the method described in embodiment 1, test result is shown in Table 1.
The performance test results of the ageing-resistant natural rubber that table 1 embodiment of the present invention and comparative example obtain
As can be seen from Table 1, the ageing-resistant natural rubber that the present invention provides carries out hot air aging, ozone aging and ultraviolet
Burin-in process after-drawing strength retention and break elongation retention and all can be maintained at more than 85%, relative to the sky in comparative example
So for rubber, ageing-resistant natural rubber heat-resistant air aging property, ozone-resistant aging property and anti-ultraviolet ageing performance are the most aobvious
Writing and improve, thermogenesis performance significantly reduces simultaneously, and preparation method is simple, with low cost, it is easy to large-scale production.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. an ageing-resistant natural rubber, it is characterised in that include the component of following weight portion: dry glue meter natural rubber latex
100 parts, rare earth carboxylate 0.01～10 parts, surfactant 0.05～0.2 part, coupling agent 0.02～4 parts, coagulator 20～80
Part.
Ageing-resistant natural rubber the most according to claim 1, it is characterised in that described rare earth carboxylate be oleic acid rare earth,
Any one in rare-earth stearate, lauric acid rare earth, malic acid rare earth, citric acid rare earth, rare earth palmitate and salicylic acid rare earth
Plant or multiple mixture.
Ageing-resistant natural rubber the most according to claim 2, it is characterised in that the rare earth element in described rare earth carboxylate
For any one in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutecium, scandium and yttrium.
Ageing-resistant natural rubber the most according to claim 1, it is characterised in that described surfactant is dodecyl sulphur
Any one or a few in acid sodium, sodium lauryl sulphate, sodium lignin sulfonate and calcium lignosulfonate.
Ageing-resistant natural rubber the most according to claim 1, it is characterised in that described coupling agent is 3-aminopropyl three ethoxy
Base silane, 3-glycydoxy trimethoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicane and double-
In (γ-triethoxysilylpropyl) tetrasulfide any one or a few.
Ageing-resistant natural rubber the most according to claim 1, it is characterised in that described coagulator is wood vinegar, described wood
The pH value of vinegar liquid is 3.0～4.2.
Ageing-resistant natural rubber the most according to claim 1, it is characterised in that the quality of described natural rubber latex Ruzhong nitrogen
Content is 0.01～0.52%.
8. the preparation method of the ageing-resistant natural rubber described in claim 1～7 any one, it is characterised in that include as follows
Step:
(1) under ultrasound condition, rare earth carboxylate, surfactant and coupling agent are reacted in aqueous phase system, obtains modification
Rare earth carboxylate dispersion；
(2) described modified RE carboxylate dispersion is mixed with natural rubber latex, continue ultrasonic, obtain the resistance to of latex state
Aging natural rubber；
(3) the ageing-resistant natural rubber of described latex state is mixed with coagulator, after solidification, obtain ageing-resistant natural rubber.
Preparation method the most according to claim 8, it is characterised in that also include after described solidification being dried, described dry
Mode is: the product after described solidification is dried 1～30 day under field conditions (factors), be then dried under the conditions of 40～80 DEG C 2～
48h。
10. preparation method described in the ageing-resistant natural rubber utilized described in claim 1～7 or claim 8～9 obtains
The sizing material prepared of ageing-resistant natural rubber, it is characterised in that include the component of following weight portion: the ageing-resistant natural rubber of dry glue meter
100 parts of glue, zinc oxide 4～6 parts, stearic acid 1～3 parts, the yellow amide 0.5 of the N-tert-butyl group-2-[4-morpholinodithio time～1 part, sulfur 2～
2.5 parts, white carbon black 30～40 parts.
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| CN108164767A (en) * | 2018-02-10 | 2018-06-15 | 中国热带农业科学院农产品加工研究所 | A kind of odorless natural rubber and preparation method thereof and a kind of sizing material |
| CN109971047A (en) * | 2019-04-02 | 2019-07-05 | 中国热带农业科学院农产品加工研究所 | A kind of natural rubber-white carbon black composite material and its preparation method and application |
| CN110372812A (en) * | 2019-07-30 | 2019-10-25 | 青岛金瑞纳橡胶科技有限公司 | A kind of natural rubber and preparation method thereof with high PO, PRI |
| CN111349184A (en) * | 2018-12-20 | 2020-06-30 | 北京万向新元科技股份有限公司 | Thermo-oxidative aging resistant natural rubber, preparation method thereof and natural rubber product |
| CN112662022A (en) * | 2020-12-10 | 2021-04-16 | 合肥学院 | Preparation method of high-resilience antibacterial sponge for sofa |
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| CN108164767B (en) * | 2018-02-10 | 2019-11-19 | 中国热带农业科学院农产品加工研究所 | A kind of odorless natural rubber and preparation method thereof and a kind of sizing material |
| CN111349184A (en) * | 2018-12-20 | 2020-06-30 | 北京万向新元科技股份有限公司 | Thermo-oxidative aging resistant natural rubber, preparation method thereof and natural rubber product |
| CN111349184B (en) * | 2018-12-20 | 2022-04-26 | 万向新元科技股份有限公司 | Thermo-oxidative aging resistant natural rubber, preparation method thereof and natural rubber product |
| CN109971047A (en) * | 2019-04-02 | 2019-07-05 | 中国热带农业科学院农产品加工研究所 | A kind of natural rubber-white carbon black composite material and its preparation method and application |
| CN109971047B (en) * | 2019-04-02 | 2021-06-01 | 中国热带农业科学院农产品加工研究所 | Natural rubber-white carbon black composite material and preparation method and application thereof |
| CN110372812A (en) * | 2019-07-30 | 2019-10-25 | 青岛金瑞纳橡胶科技有限公司 | A kind of natural rubber and preparation method thereof with high PO, PRI |
| CN112662022A (en) * | 2020-12-10 | 2021-04-16 | 合肥学院 | Preparation method of high-resilience antibacterial sponge for sofa |
| CN115028758A (en) * | 2022-06-23 | 2022-09-09 | 云南省热带作物科学研究所 | Latex treatment method for improving drying efficiency of low-protein natural rubber |
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