CN108485240A - Polyurethane elastomer material and its preparation method and application - Google Patents
Polyurethane elastomer material and its preparation method and application Download PDFInfo
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/10—Footwear characterised by the material made of rubber
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention belongs to technical field of polymer materials, it is related to a kind of polyurethane elastomer material and its preparation method and application.Polyurethane elastomer material provided by the invention is mainly made by the raw material of following parts by weight：0.01~2 part of 10~100 parts of thermoplastic polyurethane elastomer, 5~50 parts of blending-type polyurethane elastomer, 0.2~4 part of vulcanizing system, 0.2~4 part of accelerating agent, 0.01~2 part of antioxidant, 0.01~2 part of anti-aging agent, 0.01~2 part of stabilizer and anti-hydrolysis agent.The polyurethane elastomer material is using thermoplastic polyurethane elastomer as continuous phase, using blending-type polyurethane elastomer as dispersed phase, excellent combination property dynamic-vulcanization thermoplastic polyurethane elastomer material.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of polyurethane elastomer material and preparation method thereof
And application.
Background technology
Polyurethane elastomer refers to containing more carbamate groups functional group (NH-CO-O-) on macromolecular main chain
A kind of elastomer polymer, be typical segmented copolymer, with wearability is good, hardness range is wide, intensity is high, elongation
The advantages that rate is high, load support capacity is big, good damping effect, resistance to low temperature and oil-resistant weather-resistant energy are excellent.According to processing side
The difference of method, polyurethane elastomer generally can be divided into thermoplastic polyurethane elastomer (TPU), casting type polyurethane elastomer
(CPU) and blending-type polyurethane elastomer (MPU).
TPV is the abbreviation of ThermoplasticVulcanizate, and Chinese is thermoplasticity EPDM dynamic vulcanization
Elastomer or thermoplasticity EPDM dynamic perduren；When TPV generally refers to thermoplastic resin with blend rubber, rubber phase exists
Crosslinking agent effect issues biochemical cross-linking vulcanized, and is acted on by strong mechanical shearing, is sheared and is broken into a large amount of micron orders
Cross-linked rubbery particle, a kind of composite material being dispersed in thermoplastic resin.It physical property under TPV room temperature and is functionally similar to
Thermoset rubber shows as the characteristic of thermoplastic at high temperature, can be with fast, economical and easily machine-shaping.TPV has
There are the heat resistance and low compression deformation performance of vulcanized rubber, but does not need special sulfuration process.Occur at present a variety of
The all good TPV material of performance.
The most widely used TPV material is by continuous phase and EPDM ethylene propylene diene rubbers of PP analog thermoplastics resin at present
The composite material of dispersed phase.In the prior art, there are poor processabilities for dynamic vulcanization TPV material, and processing and forming is difficult, influences material
The defects of expecting performance；In addition, being ground at present for the application of the modification of Thermoplastic polyurethane elastomer material or its composite material
Study carefully more, but current research, only for application of function in a certain respect, research range is limited.So far, for
There is not been reported for the correlative study of dynamic-vulcanization thermoplastic polyurethane elastomer material (TPUV).
In consideration of it, special propose the present invention.
Invention content
The first object of the present invention is to provide one kind using thermoplastic polyurethane elastomer as continuous phase, with the poly- ammonia of mixed milling type
Ester elastomer is dispersed phase, excellent combination property dynamic-vulcanization thermoplastic polyurethane elastomer material.
The second object of the present invention is to provide a kind of preparation method of polyurethane elastomer material, this method technological process
Simply, condition is easily-controllable, of low cost, low for equipment requirements, is suitable for industrialized production.
The third object of the present invention is to provide a kind of cable comprising above-mentioned polyurethane elastomer material, tire, conveying
Band, footwear or bedding, thus these products at least have the advantages that identical as above-mentioned polyurethane elastomer material.
The fourth object of the present invention is to provide a kind of application of polyurethane elastomer material, which has
Excellent comprehensive performance, machinability is good, can cut out control property it is strong, elasticity it is good, it is thus possible to apply in cable, tire, conveyer belt, shoes
In the products such as tool or bedding.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of polyurethane elastomer material, mainly by following parts by weight
Raw material be made：
10~100 parts of thermoplastic polyurethane elastomer, 5~50 parts of blending-type polyurethane elastomer, vulcanizing system 0.2~4
Part, 0.2~4 part of accelerating agent, 0.01~2 part of antioxidant, 0.01~2 part of anti-aging agent, 0.01~2 part of stabilizer and anti-hydrolysis agent
0.01~2 part.
As further preferred technical solution, mainly it is made by the raw material of following parts by weight：
20~80 parts of thermoplastic polyurethane elastomer, 10~40 parts of blending-type polyurethane elastomer, vulcanizing system 0.5~2
Part, 0.5~2 part of accelerating agent, 0.02~1 part of antioxidant, 0.02~1 part of anti-aging agent, 0.02~1 part of stabilizer and anti-hydrolysis agent
0.02~1 part.
As further preferred technical solution, the thermoplastic polyurethane elastomer includes polyester-type thermoplastic polyurethane bullet
Property body and/or Polyether-type thermoplastic polyurethane elastomer.
As further preferred technical solution, the blending-type polyurethane elastomer includes polyester blending-type polyurethane elasticity
Body and/or polyethers blending-type polyurethane elastomer.
As further preferred technical solution, the vulcanizing system includes the component of following parts by weight：
0.1~2 part of stearic acid, 0.5~4 part of zinc stearate, 5~40 parts of precipitated silica, 0.5~3 part of silane coupling agent,
1~10 part of coumarone indene resin, 1~6 part of vulcanizing agent, 0.5~4 part of activating agent, 0.5~4 part of accelerant MBT, accelerant MBT S0.5
~4 parts and 0~3 part of antioxidant；
Preferably, the vulcanizing system includes the component of following parts by weight：
0.2~1.8 part of stearic acid, 0.8~3 part of zinc stearate, 6~35 parts of precipitated silica, silane coupling agent 0.8~
2.5 parts, 2~8 parts of coumarone indene resin, 2~5 parts of vulcanizing agent, 0.8~3.5 part of activating agent, 0.8~3.5 part of accelerant MBT, promote
0.1~2.5 part of agent MBTS0.8~3.5 part and antioxidant.
As further preferred technical solution, the accelerating agent includes captax, altax, accelerant N A and promotion
At least one of agent CZ；
Preferably, the antioxidant includes four [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic acid
Ester] pentaerythritol ester, N, bis- [[3- (3,5)--4 hydroxy phenyl of the di-t-butyl] propiono] hexamethylene diamines of N ' -, three [2,4-
Di-tert-butyl-phenyl] phosphite ester, diphosphorous acid pentaerythrite tristearin alcohol ester and β-(3,5- di-t-butyl -4- hydroxy benzenes
At least one of base) propionic acid n-octadecyl alcohol ester；
Preferably, the anti-aging agent includes N- phenyl-α-aniline, N- phenyl-β-naphthylamines, N- phenyl-N '-
Cyclohexyl p-phenylenediamine and N, at least one of N '-diphenyl-p-phenylenediamines；
Preferably, the stabilizer includes at least one in zinc stearate, calcium stearate, ethylene stearoylketene amine and silicone powder
Kind；
Preferably, the anti-hydrolysis agent include in carbodiimides, double carbide imine and polycarbodiimide at least
It is a kind of.
According to another aspect of the present invention, the present invention provides the preparation of the polyurethane elastomer material described in more than one
Method includes the following steps：
Each raw material of formula ratio is put into mixer and carries out mixing, obtains mixed material；
The mixed material is squeezed out in screw machine, is granulated to get the polyurethane elastomer material.
As further preferred technical solution, the rotating speed of screw machine is 100~600 revs/min；The temperature of mixing and/or extrusion
Degree is 100~200 DEG C.
According to another aspect of the present invention, include above-described polyurethane elastomer material the present invention also provides one kind
Cable, tire, conveyer belt, footwear or bedding.
According to another aspect of the present invention, the present invention also provides the polyurethane elastomer materials described in more than one to make
Application in standby cable, tire, conveyer belt, footwear or bedding.
Compared with prior art, the beneficial effects of the present invention are：
1, the present invention is using thermoplastic polyurethane elastomer as continuous phase, using blending-type polyurethane elastomer as dispersed phase, together
When be added to the other components such as suitable and suitable vulcanizing system, accelerating agent, the dynamic sulphur of excellent combination property has been prepared
Change Thermoplastic polyurethane elastomer material；Also, polyurethane elastomer material obtained have can cut out control property it is strong, two-phase it is compatible
Property it is good, processing performance is good, easily processed into type, elasticity it is good the advantages that.
2, the present invention is using suitable and suitable thermoplastic polyurethane elastomer, blending-type polyurethane elastomer, vulcanization body
System, accelerating agent, antioxidant, anti-aging agent, stabilizer and anti-hydrolysis agent are acted on by the coordinated of above-mentioned raw materials, can be assigned
The good processing performance of the polyurethane elastomer material, dispersing uniformity and excellent mechanical property, can cut out control property, elasticity,
The performances such as ageing-resistant, hydrolysis extend its service life, make it have excellent comprehensive performance；Meanwhile raw material of the present invention comes
Source is wide, of low cost, environmentally protective, environmentally safe, can reduce the overall cost of polyurethane elastomer material, widen
Its application range.
3, preparation method of the invention, simple for process, preparation process is easily operated, and actual application value is high, environmental-friendly,
Production efficiency is high, and product quality obtained is stablized, and is suitble to industrialization large-scale production.
4, cable, tire, conveyer belt, footwear or bedding of the invention include above-mentioned polyurethane elastomer material, thus this
A little products at least have the advantages that identical as above-mentioned polyurethane elastomer material.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
In a first aspect, a kind of polyurethane elastomer material is provided at least one embodiment, mainly by following parts by weight
Raw material be made：
10~100 parts of thermoplastic polyurethane elastomer, 5~50 parts of blending-type polyurethane elastomer, vulcanizing system 0.2~4
Part, 0.2~4 part of accelerating agent, 0.01~2 part of antioxidant, 0.01~2 part of anti-aging agent, 0.01~2 part of stabilizer and anti-hydrolysis agent
0.01~2 part.
In view of existing TPV material mostly using PP analog thermoplastics resin as continuous phase and with EPDM ethylene propylene diene rubbers be point
Dephasing, there are poor processability, processing and forming is difficult, the defects of influencing material property；And use thermoplastic polyurethane elastomer
(hereinafter referred to as TPU) is that the dynamic-vulcanization thermoplastic polyurethane elastomer material (hereinafter referred to as TPUV) of continuous phase not yet appears in the newspapers
Road, inventor study and explore through a large number of experiments, it is proposed that one kind is using TPU as continuous phase, with blending-type polyurethane elasticity
Body (hereinafter referred to as MPU) is dispersed phase, while being added to the other components such as suitable and suitable vulcanizing system, accelerating agent, is prepared
The TPUV of excellent combination property is obtained；Also, control property is strong, and the compatibility of two-phase is good, processability with that can cut out by TPUV obtained
The advantages that energy is good, easily processed into type, and elasticity is good, and then problems of the prior art have been effectively relieved.
Meanwhile the present invention is using suitable and suitable TPU, MPU, vulcanizing system, accelerating agent, antioxidant, anti-aging agent, stabilization
Agent and anti-hydrolysis agent are acted on by the coordinated of above-mentioned raw materials, can assign the good processing performances of the TPUV, be uniformly dispersed
Property and excellent mechanical property, control property, the performances such as elasticity, ageing-resistant, hydrolysis can be cut out, extend its service life, make it
With excellent comprehensive performance；Above-mentioned raw materials source is wide, of low cost, environmentally protective, environmentally safe, can reduce poly- ammonia
The overall cost of ester elastomer material has widened its application range.
In above-mentioned TPUV, TPU is good with wearability, hardness range is wide, good toughness, elasticity are good, high-strength as continuous phase
It is the features such as degree and elongation at break, good damping effect, good oil resistance, safe and environment-friendly.It counts in parts by weight, TPU is typical but non-
Restrictive content is 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or 100 parts.
In above-mentioned TPUV, MPU is as dispersed phase, with good wear-resisting property, mechanical property, oil resistance and resistance to old
The features such as changing performance, solvent resistance, resistance to low temperature and anti-hydrolytic performance, it is safe and environment-friendly.Using TPU as continuous phase, with
MPU is as dispersed phase, and the compatibility of two-phase is good, is uniformly dispersed, and processing performance is good.It counts in parts by weight, MPU is typical but unrestricted
Property content be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.
In above-mentioned TPUV, vulcanizing system can vulcanize the MPU phases in TPU/MPU blends so that MPU is in TPU continuous phases
In network-like distribution；It further, can be with the resistance to old of reinforcing material while ensureing Material Physics satisfactory mechanical property
The property changed and toughness.Count in parts by weight, the typical but non-limiting content of vulcanizing system be 0.2 part, 0.4 part, 0.5 part, 0.6
Part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 3 parts, 3.5 parts or 4 parts.
In above-mentioned TPUV, accelerating agent shortens the reaction time with that can improve reaction rate, reduces processing temperature, improves
Additive is reacted with polyurethane, reduces vulcanizing agent dosage, reduces cost, and the works such as physical mechanical property for improving rubber
With.Count in parts by weight, the typical but non-limiting content of accelerating agent be 0.2 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1
Part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 3 parts, 3.5 parts or 4 parts.
In above-mentioned TPUV, antioxidant can prevent the aging of polymer, help that polyurethane material is made to be not easy in air
Oxidation, keeps the excellent performance of material, extends the service life of material.It counts in parts by weight, antioxidant is typical but non-limiting
Content be 0.01 part, 0.02 part, 0.04 part, 0.05 part, 0.06 part, 0.08 part, 0.1 part, 0.15 part, 0.2 part, 0.3 part,
0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts or 2 parts.
In above-mentioned TPUV, anti-aging agent can improve the processing stability of material and long-term antioxidant effect.By weight
Number meter, the typical but non-limiting content of anti-aging agent be 0.01 part, 0.02 part, 0.04 part, 0.05 part, 0.06 part, 0.08 part,
0.1 part, 0.15 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts or 2 parts.
In above-mentioned TPUV, stabilizer main stabilization in system acts on, and can prevent material from being dropped in high-temperature heating process
It solves and influences material property.Count in parts by weight, the typical but non-limiting content of stabilizer be 0.01 part, 0.02 part, 0.04
Part, 0.05 part, 0.06 part, 0.08 part, 0.1 part, 0.15 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part,
1.2 parts, 1.5 parts, 1.8 parts or 2 parts.
In above-mentioned TPUV, anti-hydrolysis agent can improve the anti-hydrolytic performance of material, effectively material can be inhibited to draw because of hydrolysis
The mechanical properties decrease risen improves material viscosity decline, xanthochromia, problems of crack caused by hydrolysis, can extend product use
Service life.Count in parts by weight, the typical but non-limiting content of anti-hydrolysis agent be 0.01 part, 0.02 part, 0.04 part, 0.05 part,
0.06 part, 0.08 part, 0.1 part, 0.15 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5
Part, 1.8 parts or 2 parts.
It should be noted that the present invention for TPU, MPU, vulcanizing system, accelerating agent, antioxidant, anti-aging agent, stabilizer and
The source of anti-hydrolysis agent does not have special limitation, using each raw material well-known to those skilled in the art；Such as it may be used
Its commercial goods can also voluntarily be prepared using preparation method well known to those skilled in the art.
In a preferred embodiment, polyurethane elastomer material is mainly made by the raw material of following parts by weight：
20~80 parts of thermoplastic polyurethane elastomer, 10~40 parts of blending-type polyurethane elastomer, vulcanizing system 0.5~2
Part, 0.5~2 part of accelerating agent, 0.02~1 part of antioxidant, 0.02~1 part of anti-aging agent, 0.02~1 part of stabilizer and anti-hydrolysis agent
0.02~1 part；
Preferably, polyurethane elastomer material is mainly made by the raw material of following parts by weight：Thermoplastic polyurethane elastomer
30~70 parts, 15~35 parts of blending-type polyurethane elastomer, 0.8~1.5 part of vulcanizing system, 0.8~1.5 part of accelerating agent, antioxygen
0.05~0.8 part of 0.05~0.8 part of agent, 0.05~0.8 part of anti-aging agent, 0.05~0.8 part of stabilizer and anti-hydrolysis agent.
By advanced optimizing the content proportion relation of each material component, can further improve TPUV cut out control property it is strong,
Elasticity and resistance to ag(e)ing, stability and excellent processing performance and mechanical property etc..
In a preferred embodiment, the thermoplastic polyurethane elastomer includes polyester-type thermoplastic polyurethane bullet
Property body and/or Polyether-type thermoplastic polyurethane elastomer.
In a preferred embodiment, the blending-type polyurethane elastomer includes polyester blending-type polyurethane elasticity
Body and/or polyethers blending-type polyurethane elastomer.
It is understood that polyester-type commonly used in the art and/or polyether-type thermoplastic may be used in above-mentioned TPU and MPU
Property polyurethane elastomer and polyester-type and/or polyether-type blending-type polyurethane elastomer, the present invention do not do this excessive restriction.
In a preferred embodiment, the vulcanizing system includes the component of following parts by weight：
0.1~2 part of stearic acid, 0.5~4 part of zinc stearate, 5~40 parts of precipitated silica, 0.5~3 part of silane coupling agent,
1~10 part of coumarone indene resin, 1~6 part of vulcanizing agent, 0.5~4 part of activating agent, 0.5~4 part of accelerant MBT, accelerant MBT S0.5
~4 parts and 0~3 part of antioxidant；
Preferably, the vulcanizing system includes the component of following parts by weight：
0.2~1.8 part of stearic acid, 0.8~3 part of zinc stearate, 6~35 parts of precipitated silica, silane coupling agent 0.8~
2.5 parts, 2~8 parts of coumarone indene resin, 2~5 parts of vulcanizing agent, 0.8~3.5 part of activating agent, 0.8~3.5 part of accelerant MBT, promote
0.1~2.5 part of agent MBTS0.8~3.5 part and antioxidant
It is highly preferred that the vulcanizing system includes the component of following parts by weight：
0.5~1.5 part of stearic acid, 1~2.5 part of zinc stearate, 10~30 parts of precipitated silica, silane coupling agent 1~2
Part, 3~7 parts of coumarone indene resin, 3~4 parts of vulcanizing agent, 1~3 part of activating agent, 1~3 part of accelerant MBT, accelerant MBT S1~3
0.2~2 part of part and antioxidant.
The vulcanizing system formed under said components and dosage is applied in polyurethane elastomer material, is sent out with other components
Raw synergistic effect, can further enhance resistance to ag(e)ing, toughness, mechanical performance, mechanical property of material etc..
What needs to be explained here is that stearic acid, zinc stearate, precipitated silica, silicon in the above-mentioned vulcanizing system of the present invention
Alkane coupling agent, coumarone indene resin, vulcanizing agent, accelerant MBT, the source of accelerant MBT S and antioxidant and more specific type do not have
There is special limitation, using each raw material well-known to those skilled in the art；Its commercial goods such as may be used, it can also
It is voluntarily prepared using preparation method well known to those skilled in the art.
Optionally, above-mentioned antioxidant includes but not limited to phenolic antioxidant, amine antioxidants and phosphite ester kind antioxidant
In any one or more.
In a preferred embodiment, the accelerating agent includes captax, altax, accelerant N A and promotion
At least one of agent CZ；
Preferably, the antioxidant includes four [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic acid
Ester] pentaerythritol ester, N, bis- [[3- (3,5)--4 hydroxy phenyl of the di-t-butyl] propiono] hexamethylene diamines of N ' -, three [2,4-
Di-tert-butyl-phenyl] phosphite ester, diphosphorous acid pentaerythrite tristearin alcohol ester and β-(3,5- di-t-butyl -4- hydroxy benzenes
At least one of base) propionic acid n-octadecyl alcohol ester；
Preferably, the anti-aging agent includes N- phenyl-α-aniline, N- phenyl-β-naphthylamines, N- phenyl-N '-
Cyclohexyl p-phenylenediamine and N, at least one of N '-diphenyl-p-phenylenediamines；
Preferably, the stabilizer includes at least one in zinc stearate, calcium stearate, ethylene stearoylketene amine and silicone powder
Kind；
Preferably, the anti-hydrolysis agent include in carbodiimides, double carbide imine and polycarbodiimide at least
It is a kind of.
By the addition of above-mentioned accelerating agent, antioxidant, anti-aging agent, stabilizer and anti-hydrolysis agent, material can be further promoted
Anti-oxidant, ageing-resistant, anti-hydrolysis, processing performance, mechanical performance for expecting etc. so that material has more excellent comprehensive performance,
Prolong the service life, expands its application range.
Second aspect provides a kind of preparation method of the polyurethane elastomer material, includes the following steps：
Each raw material of formula ratio is put into mixer and carries out mixing, obtains mixed material；
The mixed material is squeezed out in screw machine, is granulated to get the polyurethane elastomer material.
Above-mentioned preparation method, easy to operate, easy to implement, preparation process is easy to control, and production efficiency is high, environmental-friendly,
And the product quality stability being prepared is good, is suitble to industrialization large-scale production.
In a preferred embodiment, the rotating speed of screw machine is 100~600 revs/min；The temperature of mixing and/or extrusion
Degree is 100~200 DEG C.
Under the operating conditions described above using above-mentioned raw materials, it carries out preparing polyurethane elastomer material, helps to improve poly- ammonia
Ester elastomer material cuts out the performances such as control property, elasticity, processing performance, mechanical property so that polyurethane elastomer material has
Excellent comprehensive performance.
The third aspect, provide in some embodiments a kind of cable comprising above-described polyurethane elastomer material,
Tire, conveyer belt, footwear or bedding.
Fourth aspect, provide in some embodiments polyurethane elastomer material described in more than one prepare cable,
Application in tire, conveyer belt, footwear or bedding.
Above-mentioned polyurethane elastomer material can be applied in all kinds of cable materials, tire, conveyer belt, footwear or bedding etc.,
Have a wide range of application；Meanwhile above-mentioned cable, tire, conveyer belt, footwear or bedding include above-mentioned polyurethane elastomer material, because
And these products at least have the advantages that it is identical as above-mentioned polyurethane elastomer material.
With reference to specific embodiment and comparative example, the invention will be further described.
Embodiment 1
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
60 parts of polyester-type thermoplastic polyurethane elastomer, 30 parts of polyester-type blending-type polyurethane elastomer, vulcanizing system 1
Part, 1 part of captax, antioxidant four [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic ester] Ji Wusi
0.5 part of alcohol ester, anti-aging agent N- phenyl-α -0.5 part of aniline, 0.5 part of stabilizer zinc stearate and anti-hydrolysis agent carbodiimides
0.5 part；
Wherein, the vulcanizing system includes the component of following parts by weight：
1 part of stearic acid, 1.5 parts of zinc stearate, 20 parts of precipitated silica, 1.5 parts of silane coupling agent, 5 parts of coumarone indene resin,
1 part of 3.5 parts of vulcanizing agent, 2 parts of activating agent, 2 parts of accelerant MBT, S2 parts of accelerant MBT and antioxidant.
Embodiment 2
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
80 parts of polyester-type thermoplastic polyurethane elastomer, 38 parts of polyester-type blending-type polyurethane elastomer, vulcanizing system 1.8
Part, 1.8 parts of captax, [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic ester] season penta of antioxidant four
Four 0.8 part of alcohol esters, anti-aging agent N- phenyl-α -0.8 part of aniline, 0.8 part of stabilizer zinc stearate and anti-hydrolysis agent carbonization two are sub-
0.8 part of amine；
Wherein, vulcanizing system is same as Example 1.
Embodiment 3
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
100 parts of Polyether-type thermoplastic polyurethane elastomer, 50 parts of polyester-type blending-type polyurethane elastomer, vulcanizing system
3.5 parts, 3.5 parts of altax, antioxidant N, N '-bis- [[3- (3,5)--4 hydroxy phenyl of di-t-butyl] propionos] oneself two
2 parts of amine, 2 parts of anti-aging agent N- phenyl-β-naphthylamines, 1.8 parts of stabilizer calcium stearate and anti-hydrolysis agent double carbide imine 1.8
Part；
Wherein, vulcanizing system is same as Example 1.
Embodiment 4
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
20 parts of Polyether-type thermoplastic polyurethane elastomer, 9 parts of polyether-type blending-type polyurethane elastomer, vulcanizing system 0.2
Part, altax and 0.2 part of captax, 0.05 part of antioxidant three [2,4- di-tert-butyl-phenyl] phosphite ester, anti-aging agent N-
Phenyl-N ' -0.05 part of cyclohexyl p-phenylenediamine, 0.05 part of stabilizer ethylene stearoylketene amine and anti-hydrolysis agent polycarbodiimide
0.05 part；
Wherein, vulcanizing system is same as Example 1.
Embodiment 5
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
50 parts of polyester-type thermoplastic polyurethane elastomer, 30 parts of polyether-type blending-type polyurethane elastomer, vulcanizing system 0.3
Part, accelerant N A and 0.3 part of accelerant CZ, 0.1 part of antioxidant diphosphorous acid pentaerythrite tristearin alcohol ester, anti-aging agent N, N '-two
0.15 part of 0.2 part of phenyl-pphenylenediamine, 0.1 part of stabilizer silicone powder and anti-hydrolysis agent double carbide imine；
Wherein, vulcanizing system is same as Example 1.
Embodiment 6
A kind of polyurethane elastomer material, with embodiment 1 difference lies in：
Vulcanizing system includes the component of following parts by weight：
1.5 parts of stearic acid, 2.5 parts of zinc stearate, 32 parts of precipitated silica, 2 parts of silane coupling agent, 6 parts of coumarone indene resin,
2 parts of 4 parts of vulcanizing agent, 3 parts of activating agent, 3 parts of accelerant MBT, S3 parts of accelerant MBT and antioxidant.
The preparation method of polyurethane elastomer material described in embodiment 1-6, includes the following steps：
Each raw material of formula ratio is put into mixer and carries out mixing, obtains mixed material；
Mixed material is squeezed out in screw machine, is granulated to get the polyurethane elastomer material；
Wherein, the rotating speed of screw machine is 400 revs/min；The temperature of mixing and extrusion is 160 DEG C.
Embodiment 7
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
55 parts of Polyether-type thermoplastic polyurethane elastomer, 28 parts of polyether-type blending-type polyurethane elastomer, vulcanizing system 2.5
Part, accelerant CZ and 2 parts of captax, antioxidant β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester
1.2 parts, anti-aging agent N- phenyl-N ' -1.2 parts of cyclohexyl p-phenylenediamine, 1.2 parts of stabilizer ethylene stearoylketene amine and resistant to hydrolysis
1 part of agent polycarbodiimide；
Wherein, the vulcanizing system includes the component of following parts by weight：
1.8 parts of stearic acid, 3 parts of zinc stearate, 35 parts of precipitated silica, 2.5 parts of silane coupling agent, 8 parts of coumarone indene resin,
2.5 parts of 5 parts of vulcanizing agent, 3.5 parts of activating agent, 3.5 parts of accelerant MBT, S3.5 parts of accelerant MBT and antioxidant.
The preparation method of polyurethane elastomer material described in embodiment 7, includes the following steps：
Each raw material of formula ratio is put into mixer and carries out mixing, obtains mixed material；
Mixed material is squeezed out in screw machine, is granulated to get the polyurethane elastomer material；
Wherein, the rotating speed of screw machine is 500 revs/min；The temperature of mixing is 100 DEG C, and the temperature of extrusion is 185 DEG C.
Comparative example 1
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
150 parts of polyester-type thermoplastic polyurethane elastomer, 55 parts of polyester-type blending-type polyurethane elastomer, vulcanizing system
0.1 part, 5 parts of captax, [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic ester] season of antioxidant four
4 parts of Doutrate, anti-aging agent N- phenyl-α -4 parts of aniline, 5 parts of stabilizer zinc stearate and anti-hydrolysis agent carbodiimides 5
Part；
As different from Example 1, the content of each raw material is not in range provided by the present invention for this comparative example.
Comparative example 2
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
110 parts of polyester-type thermoplastic polyurethane elastomer, 85 parts of polyester-type blending-type polyurethane elastomer, vulcanizing system 1
Part, 1 part of captax, antioxidant four [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic ester] Ji Wusi
0.5 part of alcohol ester, anti-aging agent N- phenyl-α -0.5 part of aniline, 0.5 part of stabilizer zinc stearate and anti-hydrolysis agent carbodiimides
0.5 part；
This comparative example as different from Example 1, thermoplastic polyurethane elastomer and blending-type polyurethane in this comparative example
The content of elastomer is not within the scope of the invention.
Comparative example 3
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
60 parts of polyester-type thermoplastic polyurethane elastomer, 30 parts of polyester-type blending-type polyurethane elastomer, 1 part of vulcanizing agent,
1 part of captax, antioxidant four [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythrite
0.5 part of ester, anti-aging agent N- phenyl-α -0.5 part of aniline, 0.5 part of stabilizer zinc stearate and anti-hydrolysis agent carbodiimides
0.5 part；
As different from Example 1, the vulcanizing system in this comparative example is vulcanizing agent commonly used in the art to this comparative example.
Comparative example 4
A kind of polyurethane elastomer material is mainly made by the raw material of following parts by weight：
60 parts of polyester-type thermoplastic polyurethane elastomer, 1 part of vulcanizing system, 1 part of captax, resists 30 parts of haloflex
Oxygen agent four [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic ester] 0.5 part of pentaerythritol ester, anti-aging agent
0.5 part of N- phenyl-α -0.5 part of aniline, 0.5 part of stabilizer zinc stearate and anti-hydrolysis agent carbodiimides；
This comparative example replaces with haloflex as different from Example 1, by blending-type polyurethane elastomer, i.e., with chlorine
Change polyethylene as dispersed phase.
Performance test
Tensile strength is carried out to polyurethane elastomer material made from embodiment 1-7 and comparative example 1-4 respectively, fracture is stretched
Long rate, hardness, tearing strength, elasticity, oxygen index (OI) performance test；Test result is as shown in table 1.
Wherein, tensile strength and elongation at break are tested with reference to GB/T1040 standards；Hardness is with reference to GB/
T2411 standards are tested；Tearing strength is tested with reference to GB/T529 standards；Elasticity is marked with reference to GB/T1681
What standard was tested；Oxygen index (OI) is tested with reference to ASTMD2863 standards.
1 the performance test results of table
As can be seen from Table 1, polyurethane elastomer material various aspects of performance obtained is excellent through the invention, has excellent
Mechanical property, elasticity it is good, widened its application range.And by the analysis of the embodiment of the present invention and comparative example comparison it is found that
Changing the proportioning of one or more raw materials in polyurethane elastomer material makes its raw material proportioning not in the scope of protection of the invention
It is interior, or a certain raw material therein is replaced, it can make its performance be deteriorated.Thus illustrate, limited in the present invention
Under raw material and proportioning, each raw material cooperates so that material has superior performance, enhances the performances such as elasticity, intensity.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of polyurethane elastomer material, which is characterized in that be mainly made by the raw material of following parts by weight：
10~100 parts of thermoplastic polyurethane elastomer, 0.2~4 part of vulcanizing system, promotees 5~50 parts of blending-type polyurethane elastomer
Into 0.2~4 part of agent, 0.01~2 part of antioxidant, 0.01~2 part of anti-aging agent, 0.01~2 part of stabilizer and anti-hydrolysis agent 0.01~2
Part.
2. polyurethane elastomer material according to claim 1, which is characterized in that mainly by the raw material system of following parts by weight
：
20~80 parts of thermoplastic polyurethane elastomer, 0.5~2 part of vulcanizing system, promotees 10~40 parts of blending-type polyurethane elastomer
Into 0.5~2 part of agent, 0.02~1 part of antioxidant, 0.02~1 part of anti-aging agent, 0.02~1 part of stabilizer and anti-hydrolysis agent 0.02~1
Part.
3. polyurethane elastomer material according to claim 1, which is characterized in that the thermoplastic polyurethane elastomer packet
Include polyester-type thermoplastic polyurethane elastomer and/or Polyether-type thermoplastic polyurethane elastomer.
4. polyurethane elastomer material according to claim 1, which is characterized in that the blending-type polyurethane elastomer packet
Include polyester blending-type polyurethane elastomer and/or polyethers blending-type polyurethane elastomer.
5. polyurethane elastomer material according to claim 1, which is characterized in that the vulcanizing system includes following weight
The component of number：
0.1~2 part of stearic acid, 0.5~4 part of zinc stearate, 5~40 parts of precipitated silica, 0.5~3 part of silane coupling agent, ancient horse
1~10 part of grand resin, 1~6 part of vulcanizing agent, 0.5~4 part of activating agent, 0.5~4 part of accelerant MBT, accelerant MBT S0.5~4
0~3 part of part and antioxidant；
Preferably, the vulcanizing system includes the component of following parts by weight：
0.2~1.8 part of stearic acid, 0.8~3 part of zinc stearate, 6~35 parts of precipitated silica, 0.8~2.5 part of silane coupling agent,
2~8 parts of coumarone indene resin, 2~5 parts of vulcanizing agent, 0.8~3.5 part of activating agent, 0.8~3.5 part of accelerant MBT, accelerating agent
0.1~2.5 part of MBTS0.8~3.5 part and antioxidant.
6. according to Claims 1 to 5 any one of them polyurethane elastomer material, which is characterized in that the accelerating agent includes
At least one of captax, altax, accelerant N A and accelerant CZ；
Preferably, the antioxidant includes four [methylene -3,3 ', 5- (di-t-butyl -4- hydroxy-phenies) propionic esters]
Pentaerythritol ester, N, bis- [[3- (3,5)--4 hydroxy phenyl of the di-t-butyl] propiono] hexamethylene diamines of N ' -, three [2,4- bis- uncles
Butyl phenyl] phosphite ester, diphosphorous acid pentaerythrite tristearin alcohol ester and β-(3,5- di-tert-butyl-hydroxy phenyl) third
At least one of sour positive octadecanol ester；
Preferably, the anti-aging agent includes N- phenyl-α-aniline, N- phenyl-β-naphthylamines, N- phenyl-N '-hexamethylene
Base p-phenylenediamine and N, at least one of N '-diphenyl-p-phenylenediamines；
Preferably, the stabilizer includes at least one of zinc stearate, calcium stearate, ethylene stearoylketene amine and silicone powder；
Preferably, the anti-hydrolysis agent includes at least one of carbodiimides, double carbide imine and polycarbodiimide.
7. as claim 1~6 any one of them polyurethane elastomer material preparation method, which is characterized in that including with
Lower step：
Each raw material of formula ratio is put into mixer and carries out mixing, obtains mixed material；
The mixed material is squeezed out in screw machine, is granulated to get the polyurethane elastomer material.
8. preparation method according to claim 7, which is characterized in that the rotating speed of screw machine is 100~600 revs/min；Mixing
And/or the temperature squeezed out is 100~200 DEG C.
9. including cable, tire, conveyer belt, footwear or the bedroom of claim 1~6 any one of them polyurethane elastomer material
Tool.
10. claim 1~6 any one of them polyurethane elastomer material prepare cable, tire, conveyer belt, footwear or
Application in bedding.
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| CN115160767B (en) * | 2022-07-12 | 2023-10-13 | 广东方振新材料精密组件有限公司 | Preparation method of polyurethane rubber and polyurethane rubber |
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