CN105778173B - A kind of method that gutta-percha prepares TPV with polyolefin elastomer - Google Patents
A kind of method that gutta-percha prepares TPV with polyolefin elastomer Download PDFInfo
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- CN105778173B CN105778173B CN201610223148.0A CN201610223148A CN105778173B CN 105778173 B CN105778173 B CN 105778173B CN 201610223148 A CN201610223148 A CN 201610223148A CN 105778173 B CN105778173 B CN 105778173B
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
A kind of method that gutta-percha prepares TPV with polyolefin elastomer, is related to a kind of method for preparing TPV, and the present invention relates to TPV material made from the blending of gutta-percha, processing aid and polyolefin elastomer, dynamic vulcanization.Gutta-percha is with polyolefin elastomer in the presence of high temperature, high shear force, and gutta-percha vulcanizes with sulphur, accelerator effect first, and the gutta-percha after crosslinking is dispersed in continuous polyolefin elastomer phase, forms sea-island structure.The rubber grain of crosslinking can make TPV obtain higher intensity, low permanent deformation and higher hardness.The invention preparation method technique is simple, easily operated, and material is widely used in automobile, aviation, damping, sealing, machinery instrument field, and there are stronger promotion and application to be worth.
Description
Technical field
The present invention relates to a kind of method for preparing TPV, is prepared more particularly to a kind of gutta-percha and polyolefin elastomer
TPV method.
Background technology
The natural eucommia resource in China enriches, and NATURAL DISTRIBUTION is in Hunan, Guizhou Province, river, Shan, Hubei Province, Henan Deng Di mountain areas, in the past 20 years, state
Family widelys popularize artificial growth, and planting range is expanded to reach Xinjiang south from Guangdong and Guangxi Provinces, north to Jilin, west, can planting range much surpass
Natural rubber tree is crossed, cultivated area has exceeded 3,000,000 mu at present.
The chemical composition of gutta percha is trans- Isosorbide-5-Nitrae-polyisoprene, is the cis- Isosorbide-5-Nitrae of composition-poly- isoamyl two of paragutta
The isomer of alkene, their physical property differ widely.Gutta-percha is the tough and tensile material of hide-like in room temperature, pure Du
Secondary rubber is colourless, and commercially available glue then carries a variety of colors.Pure gutta percha crystallizes at 10 DEG C, and 40~50 DEG C start to be presented with bullet
Property, easily elongation, 100 DEG C of softenings have plasticity, can recover original property after cooling.Its softening point is with plasticity with resin
Content and it is different.Natural gum segment is relatively soft, does not crystallize at normal temperatures and flexible.Compared with natural gum, gutta percha segment row
Row are neat, and compliance is poor, nonelastic at normal temperatures in crystalline state, is hard solid.Gutta percha is between rubber and plastics
Transition body, it has rubber and plastic dual character, there is their unexistent characteristics again.Gutta-percha is oxidizable in atmosphere to become fragile, therefore is making
Antioxidant should be added during standby gutta-percha, is contacted with sodium chlorate and chlorination reaction occurs.At normal temperatures, gutta percha can be dissolved in a variety of virtues
Fragrant hydrocarbon, is soluble in chlorinated hydrocabon, and aliphatic solvent is partially soluble in heating, is dissolved in acetone and ethanol seldom, not soluble in water
With most esters, it is not easy to be dissolved in gasoline.
When moderate is crosslinked, gutta percha is a kind of thermoplastic elastomer (TPE).Sealing is better than NR, low temperature shape can be used as to remember
Recall material.When highly cross-linked, it is the elastomer that physical property and chemical property are better than Hevea rubber.Its processability,
Cohesive, dynamic fatigue and electrical insulating property are better than natural gum.Because it has double bond, there is excellent blending processability again
Can, resulting various performances are different, the different material of purposes.
Polyolefins thermoplastic elastomer（TPO）Mainly include block copolymer, graft copolymer and the species of blend 3
Type, wherein the TPO ethene-octene copolymer synthesized using metallocene catalyst（POE）It is main
Polyolefins thermoplastic elastomer.
TPO ethene-the octene copolymer synthesized using metallocene catalyst（POE）On the one hand have
Very narrow molecular weight and short-chain branch distribution, thus there is excellent physical and mechanical properties (high resiliency, high intensity, high elongation rate)
With good cryogenic property, and because its strand is saturation, contained tertiary carbon atom is relatively fewer, thus with excellent
Resistance to thermalization and anti-ultraviolet property.POE heat endurance, optical property and anti-dry and cracked performance is better than EVA, weatherability
Better than SBS, brittle temperature is less than -76 DEG C, still has preferable toughness and ductility at low temperature, POE shearings property is good, is advantageous to
High speed extrusion and molding, seldom or plasticizer is not required to, service life is grown.POE can use peroxide, silane and method of radiating
Crosslinking, the physical and mechanical properties of material, chemical-resistant reagent and ozone resistance and EPDM are approached after crosslinking；Heat-proof aging and anti-
Ultraviolet ray ageing performance is better than EPDM and EPM, therefore POE is more suitable for outdoor use, and POE hot compression forever becomes
Shape is smaller than EPDM.POE, both can be with modified rubber as modifying agent, can also modified plastics.Due to POE processing temperature compared with
It is low, thus be relatively easy to non-polar rubber, mixing.POE maximum application is still on plastic products.With POE MODIFIED PPs,
Its notch impact strength is improved very big；Maleic anhydride is grafted to the elastomer after POE and is used for modified Pa 6, the suction of material can be made
Moist reduction, impact strength greatly improve.But there is the shortcomings that intensity, hardness are low, permanent deformation is big in POE.
Research in recent years is found, heat can be developed with polyolefin elastomer using the method gutta-percha of dynamic vulcanization
Thermoplastic elastic TPV material, improve POE low intensities, the problem of permanent deformation is big, while convenient processing.It can be widely used for vapour
In car, aviation, machinery instrument, temperature in use medium damping piece and seal.
The content of the invention
It is an object of the invention to provide a kind of method that gutta-percha and polyolefin elastomer prepare TPV, it is of the invention with
Gutta-percha vulcanizate is dispersed phase, and polyolefin elastomer is continuous phase, and it is obvious that TPV mechanics effects are made.The material has excellent
Different elasticity, higher-strength and ageing-resistant performance.After being processed using plastic working method, automobile, aviation, mechanical instrument are widely used in
The fields such as table.Its preparation method technique is simple, easily operated.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method that gutta-percha prepares TPV with polyolefin elastomer, methods described include procedure below：
（1）TPV material is prepared as raw material using gutta-percha and polyolefin elastomer, carries out batch mixing according to the following ratio：The bark of eucommia
Glue 10-90 parts, polyolefin elastomer 90-10 parts；Rubber chemicals：Stearic acid（SA）3-6 parts, zinc oxide（ZnO）4-10, prevent
Old agent 4010Na 1-4 parts, antioxidant 3-8 parts, softening agent 4-10 parts, accelerator 1-5 parts and sulphur（S）1-8 parts；
（2）It will be dried 24 hours at 50 DEG C of gutta-percha；
（3）By gutta-percha and POE, auxiliary agent, routinely technique is sequentially added in extruder, torque rheometer or banbury and moved
State vulcanizes；
（4）Blend will be granulated to be injection moulded；
（5）Blend will be granulated and carry out compression molding.
The method that a kind of described gutta-percha prepares TPV with polyolefin elastomer, the gutta-percha are planted from the bark of eucommia
Leaf, skin and fruit in thing stick up contained Gutta extraction thing, and number-average molecular weight is in 10-50 ten thousand, molecular weight distributing index PI values
1.5-3。
The method that a kind of described gutta-percha prepares TPV with polyolefin elastomer, the vulcanization accelerator is by accelerator
Two kinds in TMTD, accelerant NOBS, accelerant CZ, altax, captax, accelerator NS and sulfur-containing compound DTDM
Or two or more compositions.
The method that a kind of described gutta-percha prepares TPV with polyolefin elastomer, the age resistor is by age resistor
4010th, one or more compositions in antioxidant 4010NA, anti-aging agent RD, antioxidant 4020, antioxidant D.
The method that a kind of described gutta-percha prepares TPV with polyolefin elastomer, the softening agent are aromatic naphtha, stone
One kind in wax oil, naphthenic oil, Petropols, paraffin.
The method that a kind of described gutta-percha prepares TPV with polyolefin elastomer, the blend is in 20-60r/min
Under revolution in extruder, torque rheometer, banbury, in 120 DEG C of -170 DEG C of progress dynamic vulcanizations.
The method that a kind of described gutta-percha prepares TPV with polyolefin elastomer, the process stempressing shaping, molding
100 DEG C -150 DEG C of temperature.
Advantages of the present invention is with effect：
For the present invention to vulcanize gutta-percha as dispersed phase, POE elastomers be continuous phase, and obtained TPV performances are compared with POE intensity, resistance to
Ageing properties are improved, and the TPV permanent deformations improvement of acquisition is clearly.The TPV material has higher hard simultaneously
Degree and elasticity, and can repeat to process.It is widely used in automobile, aviation, machinery instrument field.The letter of its preparation method technique
It is single, easily operated, there are stronger promotion and application to be worth.
Brief description of the drawings
Fig. 1 gutta-percha dosage is to TPV mechanics of elastic bodies performance impact figures；
Fig. 2 gutta-percha dosage influences to scheme on TPV elastomer hardness；
The influence figure that Fig. 3 gutta-percha dosage is permanently deformed to TPV elastomers；
Fig. 4 gutta-percha dosage influences figure to 100 DEG C of ageing properties of TPV24 hours.
Embodiment
With reference to embodiment, the present invention is described in detail.
Gutta-percha and polyolefin elastomer are blended the present invention, by extruder, torque rheometer or banbury dynamic sulphur
Change, through TPV material made from injector injection or molding, there is preferable processability and elasticity, the present invention is vulcanized with gutta-percha
Glue is dispersed phase, and polyolefin elastomer is continuous phase, and it is obvious that TPV mechanics effects are made.The material have excellent resilience, compared with
High intensity and ageing-resistant performance.After being processed using plastic working method, the fields such as automobile, aviation, machinery instrument are widely used in.
Its preparation method technique is simple, easily operated.
Concretely comprise the following steps：
First gutta-percha is placed in baking oven and dried, is then plasticated and is mixed in extruder, torque rheometer or banbury
Refining, during plasticating with mixing, sequentially add POE, stearic acid（SA）, zinc oxide（ZnO）, age resistor, antioxidant, softening
Agent, accelerator and sulphur（S）, dynamic vulcanization is carried out, setting temperature is curing temperature, appropriate rotating speed, prepares gutta-percha/POE heat
Plasticity vulcanizate TPV material.The shaping of sample is carried out in injector or vulcanizing press, is injection moulded under common process
Or preheated at a certain temperature on vulcanizing press, pressurize, slice after being then cold-pressed to normal temperature.
Embodiment
（1）By gutta-percha low temperature drying（50 DEG C of dryings 24 hours）.
（2）Batch mixing is carried out according to the following ratio：Gutta-percha 0-70 parts, with 10 parts for variable, thermoplastic polyolefin resin 100-
30 parts.Other are rubber chemicals（It is shown in Table 1 formula examples）.
（3）Gutta-percha and polyolefin elastomer, auxiliary agent are added in torque rheometer, 160 DEG C of dynamic vulcanizations.
（4）By the blending TPV material vulcanizing press of gutta-percha and polyolefin elastomer in 100 DEG C of compactings.
（5）Main performance is shown in Fig. 1, Fig. 2, Fig. 3, Fig. 4.
Table 1 implements formula examples
。
Claims (1)
1. a kind of method that gutta-percha prepares TPV with polyolefin elastomer, it is characterised in that methods described includes following mistake
Journey：
（1）TPV material is prepared as raw material using gutta-percha and polyolefin elastomer, carries out batch mixing according to the following ratio：Gutta-percha
10-90 parts, polyolefin elastomer 90-10 parts；Rubber chemicals：Stearic acid（SA）3-6 parts, zinc oxide（ZnO）4-10, prevent always
Agent 4010Na 1-4 parts, antioxidant 3-8 parts, softening agent 4-10 parts, accelerator 1-5 parts and sulphur（S）1-8 parts；
（2）It will be dried 24 hours at 50 DEG C of gutta-percha；
（3）By gutta-percha and POE, auxiliary agent, routinely technique sequentially adds dynamic sulphur in extruder, torque rheometer or banbury
Change；
（4）Blend will be granulated to be injection moulded；
（5）Blend will be granulated and carry out compression molding；
Leaf, skin and the fruit that the gutta-percha is derived from bark of eucommia plant stick up contained Gutta extraction thing, and number-average molecular weight exists
10-50 ten thousand, molecular weight distributing index PI values 1.5-3；The vulcanization accelerator is by Vulcanization accelerator TMTD, accelerant NOBS, accelerator
Two or more composition in CZ, altax, captax, accelerator NS and sulfur-containing compound DTDM；It is described anti-old
Agent is made up of the one or more in antioxidant 4010, antioxidant 4010NA, anti-aging agent RD, antioxidant 4020, antioxidant D；Institute
Softening agent is stated as one kind in aromatic naphtha, paraffin oil, naphthenic oil, Petropols, paraffin；The blend turns in 20-60r/min
In several lower extruders, torque rheometer, banbury, in 120 DEG C of -170 DEG C of progress dynamic vulcanizations；The process stempressing shaping, mould
Press 100 DEG C -150 DEG C of temperature.
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| CN201610223148.0A CN105778173B (en) | 2016-04-12 | 2016-04-12 | A kind of method that gutta-percha prepares TPV with polyolefin elastomer |
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| CN201610223148.0A CN105778173B (en) | 2016-04-12 | 2016-04-12 | A kind of method that gutta-percha prepares TPV with polyolefin elastomer |
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| CN105778173B true CN105778173B (en) | 2018-03-13 |
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| CN114854162A (en) * | 2022-05-12 | 2022-08-05 | 西北工业大学 | Preparation method of heat-resistant and creep-resistant polyolefin thermoplastic elastomer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039254A (en) * | 1988-07-04 | 1990-01-31 | 中国科学院化学研究所 | High-elastic rubber products gutta percha |
| CN102827412A (en) * | 2012-09-11 | 2012-12-19 | 沈阳化工大学 | Preparation method for natural gutta rubber-toughened plastic resin |
| CN103589048A (en) * | 2013-11-08 | 2014-02-19 | 成都科兴材料与工程应用研究所 | Industrial production method of dynamic vulcanized thermoplastic polyolefin elastomer |
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- 2016-04-12 CN CN201610223148.0A patent/CN105778173B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039254A (en) * | 1988-07-04 | 1990-01-31 | 中国科学院化学研究所 | High-elastic rubber products gutta percha |
| CN102827412A (en) * | 2012-09-11 | 2012-12-19 | 沈阳化工大学 | Preparation method for natural gutta rubber-toughened plastic resin |
| CN103589048A (en) * | 2013-11-08 | 2014-02-19 | 成都科兴材料与工程应用研究所 | Industrial production method of dynamic vulcanized thermoplastic polyolefin elastomer |
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