CN106008898A - High-moisture-resistance cold/heat-resistant thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
High-moisture-resistance cold/heat-resistant thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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Abstract
The invention provides a high-moisture-resistance cold/heat-resistant thermoplastic polyurethane elastomer and a preparation method thereof. The polyurethane elastomer is mainly prepared from the following raw materials in parts by weight: 25-35 parts of diisocyanate, 50-70 parts of polylol, 5-18 parts of nano carbon fiber, 5-10 parts of cotton fiber, 10-15 parts of low-density polyethylene, 1-8 parts of chain extender and 1-3 parts of catalyst. The diisocyanate is a mixture of isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, and the polylol is a mixture of polyether glycol and polyester polyol. The tensile strength of the thermoplastic polyurethane elastomer reaches 90 MPa or above, the elongation at break reaches 970%, the rebound rate reaches 88% or above, and the moisture permeability reaches 12000-15000 g/m<2>/day. The thermoplastic polyurethane elastomer has the advantages of ultrahigh moisture resistance and favorable cold/heat resistance.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of Polyurethane Thermoplastic Elastomer and preparation method thereof, especially
Relate to Polyurethane Thermoplastic Elastomer of a kind of high moistureproof and resistance to cold and heat and preparation method thereof.
Background technology
Thermoplastic polyurethane (TPU) is a kind of novel organic polymer synthetic material, and its properties is excellent, Ke Yidai
For rubber, soft polyvinyl chloride material PVC.Such as it has the physical property of excellence, and such as wearability, resilience force is all better than general
Logical polyurethane and PVC, resistance to ag(e)ing is better than rubber, it may be said that be the optimal material substituting PVC and PU.
Along with science and technology progress, polyurethane material is had higher requirement, it is intended that its possess resistance to
Mill property, while resilience force, there is resistance to cold and heat and the function such as highly moistureproof, so that polyurethane product is at low temperature and high temperature
Its original performance is preferably kept under environment.Therefore, in this area, it is desirable to obtain a kind of poly-ammonia that moistureproof can be resistant to again cold and heat
Ester material.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of Polyurethane Thermoplastic Elastomer and preparation thereof
Method, is not the most to provide Polyurethane Thermoplastic Elastomer of a kind of high moistureproof and resistance to cold and heat and preparation method thereof.
For reaching this purpose, the present invention by the following technical solutions:
On the one hand, the present invention provides a kind of Polyurethane Thermoplastic Elastomer, described Polyurethane Thermoplastic Elastomer mainly by
Following raw material prepares:
Wherein said diisocyanate is the mixed of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate
Compound, described polyhydric alcohol is the mixture of polyether polyol and PEPA.
In the present invention, utilize two kinds of specific diisocyanate and two kinds of specific polyhydric alcohol to prepare elastic polyurethane
Body, overcomes the polyurethane bullet utilizing single polyether polyol or PEPA to produce with single di-isocyanate reaction
Gonosome is difficult to the defect being controlled soft section and hard section, by controlling specific diisocyanate and two kinds of specific polyhydric alcohol
With the proportion relation of other raw materials, soft section can be controlled and hard section has suitable proportionate relationship so that it is the polyurethane bullet obtained
Gonosome has more satisfactory elasticity, and carbon nano-fiber, cotton fiber and Low Density Polyethylene three cooperate in addition, collaborative work
With, the moisture resistance of polyurethane elastomer can be strengthened, and make it possess good cold resistance energy.
In the present invention, the consumption of described diisocyanate can be 26 weight portions, 27 weight portions, 28 weight portions, 29 weights
Amount part, 30 weight portions, 31 weight portions, 32 weight portions, 33 weight portions or 34 weight portions.
In the present invention, the consumption of described polyhydric alcohol can be 52 weight portions, 54 weight portions, 56 weight portions, 58 weight portions,
60 weight portions, 62 weight portions, 65 weight portions or 68 weight portions.
In invention, the consumption of described carbon nano-fiber can be 6 weight portions, 8 weight portions, 10 weight portions, 12 weight portions,
14 weight portions, 16 weight portions or 17 weight portions.
In the present invention, the consumption of described cotton fiber can be 6 weight portions, 6.5 weight portions, 7 weight portions, 7.5 weight portions,
8 weight portions, 8.5 weight portions, 9 weight portions or 9.5 weight portions.
In the present invention, the consumption of described Low Density Polyethylene can be 11 weight portions, 11.5 weight portions, 12 weight portions,
12.5 weight portions, 13 weight portions, 13.5 weight portions, 14 weight portions or 14.5 weight portions.
In the present invention, the consumption of described chain extender can be 2 weight portions, 3 weight portions, 4 weight portions, 5 weight portions, 6 weights
Amount part or 7 weight portions.
In the present invention, the consumption of described catalyst can be 1.3 weight portions, 1.5 weight portions, 1.8 weight portions, 2 weight
Part, 2.3 weight portions, 2.5 weight portions or 2.8 weight portions.
Preferably, described Polyurethane Thermoplastic Elastomer is mainly prepared by following raw material:
In the present invention, isophorone diisocyanate and hydrogenated diphenyl methane two Carbimide. in described diisocyanate
The mass ratio of ester is (2-5): 1, such as 2:1,2.5:1,3:1,3.5:1,4:1,4.5:1 or 5:1, preferably (3-4): 1.
Preferably, in described polyhydric alcohol, the mass ratio of polyether polyol and PEPA is 1:(1-3), such as 1:1,1:
1.3,1:1.5,1:1.8,1:2,1:2.3,1:2.5,1:2.8 or 1:3.
Preferably, the number-average molecular weight of described polyhydric alcohol is 2500-4000, such as 2500,2800,3000,3300,
3500,3800 or 4000.
Preferably, any one during described chain extender is ethylene glycol, 1,3-PD, BDO or 1,5-PD
Plant or the combination of at least two.
Preferably, during described catalyst is stannous octoate, two sad two fourth stannum or moon silicic acid two fourth stannum any one or
The combination of at least two.
In the present invention by controlling the consumption proportion of two kinds of diisocyanate, and the consumption proportion of two kinds of polyhydric alcohol,
And with the use of rice carbon fiber, cotton fiber and Low Density Polyethylene, each component cooperates, synergism so that polyurethane
Elastomer has good elasticity, good processability, and carbon nano-fiber, cotton fiber and Low Density Polyethylene three
Cooperate, synergism, the moisture resistance of polyurethane elastomer can be strengthened, and make it possess good cold resistance energy.
On the other hand, the invention provides method for preparing thermoplastic polyurethane elastomer as above, described method
Comprise the following steps:
(1) diisocyanate, polyhydric alcohol, chain extender, catalyst are added in container, under agitation, vacuum dehydration,
Then at 100-120 DEG C (such as 103 DEG C, 105 DEG C, 108 DEG C, 110 DEG C, 113 DEG C, 115 DEG C or 118 DEG C) reaction 2-4h (such as
2.3h, 2.5h, 2.8h, 3h, 3.3h, 3.5h or 3.8h)；
(2) in the reaction mass of step (1), carbon nano-fiber, cotton fiber and Low Density Polyethylene, mix homogeneously are added
After, utilize double screw extruder extruding pelletization to obtain described calendering grade thermoplastic polyurethane elastomer.
Preferably, temperature during step (1) described vacuum dehydration is 60-70 DEG C, such as 62 DEG C, 65 DEG C, 68 DEG C or 70 DEG C.
Preferably, the speed of step (1) described stirring is 1000-1500r/min, such as 1000r/min, 1100r/min,
1200r/min, 1300r/min, 1400r/min or 1500r/min.
Preferably, pressure during step (1) described vacuum dehydration is-0.3～-0.1kPa, such as-0.3kPa ,-
0.28kPa ,-0.25kPa ,-0.23kPa ,-0.2kPa ,-0.18kPa ,-0.15kPa ,-0.13kPa or-0.1kPa.
Preferably, the feeding section temperature of step (2) described double screw extruder is 110-120 DEG C, such as 112 DEG C, 115
DEG C, 118 DEG C or 120 DEG C, mixing section temperature is 130-150 DEG C, such as 132 DEG C, 135 DEG C, 138 DEG C, 140 DEG C, 143 DEG C, 145 DEG C
Or 148 DEG C, extruding zone temperature is 160-180 DEG C, such as 162 DEG C, 165 DEG C, 168 DEG C, 170 DEG C, 173 DEG C, 175 DEG C or 178 DEG C,
Head temperature is 150-160 DEG C, such as 153 DEG C, 155 DEG C, 158 DEG C or 160 DEG C.
As optimal technical scheme, method for preparing thermoplastic polyurethane elastomer of the present invention specifically includes following
Step:
(1) diisocyanate, polyhydric alcohol, chain extender, catalyst are added in container, stir at 1000-1500r/min rotating speed
Mix down, 60-70 DEG C of vacuum dehydration under-0.3～-0.1kPa pressure, then react 1-5h at 120-140 DEG C；
(2) in the reaction mass of step (1), carbon nano-fiber, cotton fiber and Low Density Polyethylene, mix homogeneously are added
After, utilizing double screw extruder extruding pelletization, the feeding section temperature of described double screw extruder is 110-120 DEG C, mixing section temperature
Degree is for 130-150 DEG C, and extruding zone temperature is 160-180 DEG C, and head temperature is 150-160 DEG C, obtains described pressure after extruding pelletization
Prolong grade thermoplastic polyurethane elastomer.
Relative to prior art, the method have the advantages that
The present invention uses specific diisocyanate and polyhydric alcohol, and each component, under specific consumption proportion, interacts,
Mutually coordinated so that the polyurethane prepared has good mechanical performance and processability, good springiness, and nano-sized carbon
Fiber, cotton fiber and Low Density Polyethylene three cooperate, and synergism can strengthen the moisture resistance of polyurethane elastomer,
And make it possess good cold resistance energy.After measured, the hot strength of gained polyurethane elastomer reaches more than 90MPa, disconnected
Splitting percentage elongation and reach 970%, rebound degree reaches more than 88%, and rate of perviousness reaches 12000-15000g/m2/ sky, possesses superelevation and prevents
Tide, and in the temperature changing process of-20 DEG C ,-10 DEG C, 0 DEG C, 30 DEG C and 80 DEG C, the rebound degree fluctuation of product is the least, tool
There is good cold resistance energy.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.Those skilled in the art should be bright
, the only help of described embodiment understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
In the present embodiment, polyurethane elastomer is prepared by following raw material:
Wherein said diisocyanate is the mixed of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate
Compound, in diisocyanate, the mass ratio of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate is 3:1, institute
Stating the mixture that polyhydric alcohol is polyether polyol and PEPA, the mass ratio of polyether polyol and PEPA is 1:2,
The number-average molecular weight of polyhydric alcohol is 3000, and described chain extender is ethylene glycol, and described catalyst is stannous octoate.
Preparation method is as follows:
(1) diisocyanate, polyhydric alcohol, chain extender, catalyst are added in container, stir at 1000-1500r/min rotating speed
Mix down, 60-70 DEG C of vacuum dehydration under-0.3～-0.1kPa pressure, then react 1-5h at 120-140 DEG C；
(2) in the reaction mass of step (1), carbon nano-fiber, cotton fiber and Low Density Polyethylene, mix homogeneously are added
After, utilizing double screw extruder extruding pelletization, the feeding section temperature of described double screw extruder is 110-120 DEG C, mixing section temperature
Degree is for 130-150 DEG C, and extruding zone temperature is 160-180 DEG C, and head temperature is 150-160 DEG C, obtains described pressure after extruding pelletization
Prolong grade thermoplastic polyurethane elastomer.
Embodiment 2
In the present embodiment, polyurethane elastomer is prepared by following raw material:
Wherein said diisocyanate is the mixed of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate
Compound, in diisocyanate, the mass ratio of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate is 5:1, institute
Stating the mixture that polyhydric alcohol is polyether polyol and PEPA, the mass ratio of polyether polyol and PEPA is 1:1,
The number-average molecular weight of polyhydric alcohol is 4000, and described chain extender is BDO, and described catalyst is two sad two fourth stannum.
Preparation method is as follows:
(1) diisocyanate, polyhydric alcohol, chain extender, catalyst are added in container, stir at 1000-1500r/min rotating speed
Mix down, 60-70 DEG C of vacuum dehydration under-0.3～-0.1kPa pressure, then react 1-5h at 120-140 DEG C；
(2) in the reaction mass of step (1), carbon nano-fiber, cotton fiber and Low Density Polyethylene, mix homogeneously are added
After, utilizing double screw extruder extruding pelletization, the feeding section temperature of described double screw extruder is 110-120 DEG C, mixing section temperature
Degree is for 130-150 DEG C, and extruding zone temperature is 160-180 DEG C, and head temperature is 150-160 DEG C, obtains described pressure after extruding pelletization
Prolong grade thermoplastic polyurethane elastomer.
Embodiment 3
In the present embodiment, polyurethane elastomer is prepared by following raw material:
Wherein said diisocyanate is the mixed of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate
Compound, in diisocyanate, the mass ratio of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate is 4:1, institute
Stating the mixture that polyhydric alcohol is polyether polyol and PEPA, the mass ratio of polyether polyol and PEPA is 1:3,
The number-average molecular weight of polyhydric alcohol is 2500, and described chain extender is 1,3-PD, and described catalyst is stannous octoate.
Preparation method is as follows:
(1) diisocyanate, polyhydric alcohol, chain extender, catalyst are added in container, stir at 1000-1500r/min rotating speed
Mix down, 60-70 DEG C of vacuum dehydration under-0.3～-0.1kPa pressure, then react 1-5h at 120-140 DEG C；
(2) in the reaction mass of step (1), carbon nano-fiber, cotton fiber and Low Density Polyethylene, mix homogeneously are added
After, utilizing double screw extruder extruding pelletization, the feeding section temperature of described double screw extruder is 110-120 DEG C, mixing section temperature
Degree is for 130-150 DEG C, and extruding zone temperature is 160-180 DEG C, and head temperature is 150-160 DEG C, obtains described pressure after extruding pelletization
Prolong grade thermoplastic polyurethane elastomer.
Embodiment 4
In the present embodiment, polyurethane elastomer is prepared by following raw material:
Wherein said diisocyanate is the mixed of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate
Compound, in diisocyanate, the mass ratio of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate is 2:1, institute
Stating the mixture that polyhydric alcohol is polyether polyol and PEPA, the mass ratio of polyether polyol and PEPA is 1:3,
The number-average molecular weight of polyhydric alcohol is 3000, and described chain extender is 1,5-PD, and described catalyst is moon silicic acid two fourth stannum.
Preparation method is as follows:
(1) diisocyanate, polyhydric alcohol, chain extender, catalyst are added in container, stir at 1000-1500r/min rotating speed
Mix down, 60-70 DEG C of vacuum dehydration under-0.3～-0.1kPa pressure, then react 1-5h at 120-140 DEG C；
(2) in the reaction mass of step (1), carbon nano-fiber, cotton fiber and Low Density Polyethylene, mix homogeneously are added
After, utilizing double screw extruder extruding pelletization, the feeding section temperature of described double screw extruder is 110-120 DEG C, mixing section temperature
Degree is for 130-150 DEG C, and extruding zone temperature is 160-180 DEG C, and head temperature is 150-160 DEG C, obtains described pressure after extruding pelletization
Prolong grade thermoplastic polyurethane elastomer.
Comparative example 1
This comparative example the difference is that only with embodiment 1, and diisocyanate is single isophorone diisocyanate
Ester, in addition, remaining raw material is the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 2
This comparative example the difference is that only in embodiment 1, and diisocyanate is single hydrogenated diphenyl methane two
Isocyanates, in addition, remaining raw material is the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 3
This comparative example the difference is that only in embodiment 1, isophorone diisocyanate and hydrogenated diphenyl methane
The mass ratio of diisocyanate is 1:1, in addition, remaining raw material and raw material dosage and preparation method all with embodiment 1 phase
With.
Comparative example 4
This comparative example the difference is that only in embodiment 1, isophorone diisocyanate and hydrogenated diphenyl methane
The mass ratio of diisocyanate is 6:1, in addition, remaining raw material and raw material dosage and preparation method all with embodiment 1 phase
With.
Comparative example 5
This comparative example the difference is that only in embodiment 1, and polyhydric alcohol is polyether polyol, and in addition, remaining is former
Expect the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 6
This comparative example the difference is that only in embodiment 1, and polyhydric alcohol is PEPA, and in addition, remaining is former
Expect the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 7
This comparative example the difference is that only in embodiment 1, and the mass ratio of polyether polyol and PEPA is 2:
1, in addition, remaining raw material is the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 8
This comparative example the difference is that only in embodiment 1, and the mass ratio of polyether polyol and PEPA is 1:
4, in addition, remaining raw material is the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 9
This comparative example the difference is that only in embodiment 1, and the number-average molecular weight of polyhydric alcohol is 2000, in addition,
Remaining raw material is the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 10
This comparative example the difference is that only in embodiment 1, and the number-average molecular weight of polyhydric alcohol is 4500, in addition,
Remaining raw material is the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 11
This comparative example the difference is that only in embodiment 1, does not include Nano carbon fibers in the raw material of polyurethane elastomer
Dimension, cotton fiber and Low Density Polyethylene, outside this, remaining raw material is the most same as in Example 1 with raw material dosage and preparation method.
Comparative example 12
This comparative example the difference is that only in embodiment 1, does not include Nano carbon fibers in the raw material of polyurethane elastomer
Dimension, the consumption of cotton fiber is 18 weight portions, outside this, remaining raw material and raw material dosage and preparation method all with embodiment 1 phase
With.
Comparative example 13
This comparative example the difference is that only in embodiment 1, does not include Nano carbon fibers in the raw material of polyurethane elastomer
Dimension, the consumption of Low Density Polyethylene is 23 weight portions, outside this, remaining raw material and raw material dosage and preparation method all with enforcement
Example 1 is identical.
Comparative example 14
This comparative example the difference is that only in embodiment 1, does not include that low-density is gathered in the raw material of polyurethane elastomer
Ethylene is tieed up, and the consumption of carbon nano-fiber is 23 weight portions, and outside this, remaining raw material and raw material dosage and preparation method are all with real
Execute example 1 identical.
Comparative example 15
This comparative example the difference is that only in embodiment 1, does not include that low-density is gathered in the raw material of polyurethane elastomer
Ethylene is tieed up, and the consumption of cotton fiber is 21 weight portions, and outside this, remaining raw material and raw material dosage and preparation method are all and embodiment
1 is identical.
Comparative example 16
This comparative example the difference is that only in embodiment 1, does not include cotton fiber in the raw material of polyurethane elastomer, low
The consumption of density polyethylene is 21 weight portions, outside this, remaining raw material and raw material dosage and preparation method all with embodiment 1 phase
With.
Comparative example 17
This comparative example the difference is that only in embodiment 1, does not include cotton fiber, receive in the raw material of polyurethane elastomer
The consumption of rice carbon fiber is 18 weight portions, outside this, remaining raw material and raw material dosage and preparation method all with embodiment 1 phase
With.
Comparative example 18
This comparative example the difference is that only in embodiment 1, does not include Nano carbon fibers in the raw material of polyurethane elastomer
Peacekeeping cotton fiber, the consumption of Low Density Polyethylene is 31 weight portions, outside this, remaining raw material and raw material dosage and preparation method
The most same as in Example 1.
Comparative example 19
This comparative example the difference is that only in embodiment 1, does not include Nano carbon fibers in the raw material of polyurethane elastomer
Peacekeeping Low Density Polyethylene, the consumption of cotton fiber is 31 weight portions, outside this, remaining raw material and raw material dosage and preparation method
The most same as in Example 1.
Comparative example 20
This comparative example the difference is that only in embodiment 1, the raw material of polyurethane elastomer does not include cotton fiber and
Low Density Polyethylene, the consumption of carbon nano-fiber is 31 weight portions, outside this, remaining raw material and raw material dosage and preparation method
The most same as in Example 1.
The polyurethane elastomer preparing embodiment 1-4 and comparative example 1-20 carries out performance test, result such as table 1
Shown in.
Table 1
By the result of table 1 it can be seen that polyurethane elastomer prepared by the present invention has the most elastic and mechanical performance,
Machinability is strong, and rate of perviousness is high, possesses superelevation moisture resistance.By the contrast of embodiment 1 and comparative example 1-10 it can be seen that two isocyanides
The molecular weight of acid esters and the selection of polyhydric alcohol and consumption proportion and polyhydric alcohol for polyurethane obtain good elasticity and
Mechanical performance has important function, and each component cooperates and could obtain good performance.By embodiment 1 and comparative example 11-20
Contrast it can be seen that carbon nano-fiber, cotton fiber and Low Density Polyethylene for improve polyurethane elastomer rate of perviousness tool
Having synergy, three is mutually collaborative makes the rate of perviousness of polyurethane elastomer reach 12000-15000g/m2/ sky.
Embodiment 1-4 and the elastic polyurethane of comparative example 1-20 is measured at-20 DEG C ,-10 DEG C, 0 DEG C, 30 DEG C and 80 DEG C
The change of the rebound degree of body, to investigate the performance of its resistance to cold and heat, result is as shown in table 2.
Table 2
| Rebound degree (%) | -20℃ | -10℃ | 0℃ | 30℃ | 80℃ |
| Embodiment 1 | 95 | 94 | 94 | 94 | 96 |
| Embodiment 2 | 88 | 87 | 88 | 88 | 89 |
| Embodiment 3 | 93 | 92 | 92 | 92 | 91 |
| Embodiment 4 | 90 | 92 | 90 | 90 | 91 |
| Comparative example 1 | 78 | 79 | 74 | 78 | 81 |
| Comparative example 2 | 71 | 70 | 75 | 76 | 79 |
| Comparative example 3 | 71 | 72 | 73 | 75 | 78 |
| Comparative example 4 | 73 | 70 | 76 | 78 | 79 |
| Comparative example 5 | 74 | 76 | 77 | 79 | 80 |
| Comparative example 6 | 75 | 70 | 71 | 73 | 79 |
| Comparative example 7 | 71 | 70 | 71 | 73 | 79 |
| Comparative example 8 | 75 | 77 | 78 | 79 | 80 |
| Comparative example 9 | 77 | 76 | 75 | 78 | 80 |
| Comparative example 10 | 76 | 75 | 72 | 77 | 79 |
| Comparative example 11 | 52 | 50 | 74 | 75 | 61 |
| Comparative example 12 | 55 | 54 | 78 | 79 | 60 |
| Comparative example 13 | 59 | 58 | 77 | 78 | 59 |
| Comparative example 14 | 56 | 57 | 79 | 79 | 61 |
| Comparative example 15 | 55 | 52 | 76 | 77 | 60 |
| Comparative example 16 | 54 | 56 | 79 | 78 | 62 |
| Comparative example 17 | 55 | 52 | 77 | 78 | 62 |
| Comparative example 18 | 52 | 53 | 76 | 77 | 60 |
| Comparative example 19 | 53 | 56 | 80 | 79 | 59 |
| Comparative example 20 | 53 | 55 | 79 | 80 | 61 |
By the result of table 2 it can be seen that the polyurethane elastomer prepared of the present invention-20 DEG C ,-10 DEG C, 0 DEG C, 30 DEG C and
In the temperature changing process of 80 DEG C, the rebound degree fluctuation of product is the least, illustrates that it has good cold resistance energy, when two isocyanides
During the change of molecular weight of acid esters and the selection of polyhydric alcohol and consumption proportion and polyhydric alcohol (such as comparative example 1-10), although produce
The rebound degree of product can fluctuate in the temperature changing process of-20 DEG C ,-10 DEG C, 0 DEG C, 30 DEG C and 80 DEG C, but fluctuation is not
Greatly, and when polyurethane elastomer prepare raw material does not include in carbon nano-fiber, cotton fiber and Low Density Polyethylene one,
When both or three (comparative example 11-20), the rebound degree of its polyurethane elastomer prepared-20 DEG C ,-10 DEG C, 0
DEG C, the temperature changing process of 30 DEG C and 80 DEG C can occur bigger fluctuation, the contrast by embodiment 1 with comparative example 11-20 can
To find out, carbon nano-fiber, cotton fiber and Low Density Polyethylene can have association for the cold resistance improving polyurethane elastomer
Same effect.
Applicant states, the present invention illustrates the thermoplastic poly of the moistureproof and resistance to cold and heat of height of the present invention by above-described embodiment
Urethane elastomer and preparation method thereof, but the invention is not limited in above-described embodiment, i.e. do not mean that the present invention has to rely on
Above-described embodiment could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to the present invention
The equivalence of each raw material of product is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within protection scope of the present invention
Within the scope of disclosure.
Claims (10)
1. a Polyurethane Thermoplastic Elastomer, it is characterised in that described Polyurethane Thermoplastic Elastomer is mainly by following raw material
Prepare:
Wherein said diisocyanate is the mixture of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate,
Described polyhydric alcohol is the mixture of polyether polyol and PEPA.
Polyurethane Thermoplastic Elastomer the most according to claim 1, it is characterised in that described Polyurethane Thermoplastic Elastomer
Mainly prepared by following raw material:
Polyurethane Thermoplastic Elastomer the most according to claim 1 and 2, it is characterised in that different in described diisocyanate
The mass ratio of isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate is (2-5): 1, preferably (3-4): 1.
4. according to the Polyurethane Thermoplastic Elastomer according to any one of claim 1-3, it is characterised in that in described polyhydric alcohol
The mass ratio of polyether polyol and PEPA is 1:(1-3).
5. according to the Polyurethane Thermoplastic Elastomer according to any one of claim 1-4, it is characterised in that described polyhydric alcohol
Number-average molecular weight is 2500-4000.
6. according to the Polyurethane Thermoplastic Elastomer according to any one of claim 1-5, it is characterised in that described chain extender is
Any one or the combination of at least two in ethylene glycol, 1,3-propylene glycol, 1,4-butanediol or 1,5-pentanediol；
Preferably, during described catalyst is stannous octoate, two sad two fourth stannum or moon silicic acid two fourth stannum any one or at least
The combination of two kinds.
7. according to the method for preparing thermoplastic polyurethane elastomer according to any one of claim 1-6, it is characterised in that institute
The method of stating comprises the following steps:
(1) diisocyanate, polyhydric alcohol, chain extender, catalyst are added in container, under agitation, vacuum dehydration, then
2-4h is reacted at 100-120 DEG C；
(2) in the reaction mass of step (1), carbon nano-fiber, cotton fiber and Low Density Polyethylene, after mix homogeneously, profit are added
Described calendering grade thermoplastic polyurethane elastomer is obtained with double screw extruder extruding pelletization.
Preparation method the most according to claim 7, it is characterised in that temperature during step (1) described vacuum dehydration is 60-
70℃；
Preferably, the speed of step (1) described stirring is 1000-1500r/min；
Preferably, pressure during step (1) described vacuum dehydration is-0.3～-0.1kPa.
9. according to the preparation method described in claim 7 or 8, it is characterised in that the feeding of step (2) described double screw extruder
Duan Wendu is 110-120 DEG C, and mixing section temperature is 130-150 DEG C, and extruding zone temperature is 160-180 DEG C, and head temperature is 150-
160℃。
10. according to the preparation method according to any one of claim 7-9, it is characterised in that said method comprising the steps of:
(1) diisocyanate, polyhydric alcohol, chain extender, catalyst are added in container, stir at 1000-1500r/min rotating speed
Under, 60-70 DEG C of vacuum dehydration under-0.3～-0.1kPa pressure, then react 1-5h at 120-140 DEG C；
(2) in the reaction mass of step (1), carbon nano-fiber, cotton fiber and Low Density Polyethylene, after mix homogeneously, profit are added
Using double screw extruder extruding pelletization, the feeding section temperature of described double screw extruder is 110-120 DEG C, and mixing section temperature is
130-150 DEG C, extruding zone temperature is 160-180 DEG C, and head temperature is 150-160 DEG C, obtains described calendering level after extruding pelletization
Polyurethane Thermoplastic Elastomer.
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