CN1473876A - Rectorite/thermoplastic polyurethane elastomer nano composite material and preparing method - Google Patents
Rectorite/thermoplastic polyurethane elastomer nano composite material and preparing method Download PDFInfo
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- CN1473876A CN1473876A CNA021393419A CN02139341A CN1473876A CN 1473876 A CN1473876 A CN 1473876A CN A021393419 A CNA021393419 A CN A021393419A CN 02139341 A CN02139341 A CN 02139341A CN 1473876 A CN1473876 A CN 1473876A
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Abstract
The present invention relates to processing of polymer and is especially a kind of composite nano rectorite/thermoplastic polyurethane elastomer material prepared through smelting and blending process. Owing to the surface and interface effect of the nano particle, the composite material of the present invention has its mechanical performance and heat performance superior to those of traditional composite material in the same chemical composition. The composite material is prepared with thermoplastic polyurethane elastomer of different kinds 100-150 weight portions, organic rectorite clay 1-10 weight portions and demolding agent 1-5 weight portions and through simple pollution-less smelting and blending process. The composite material has wide application.
Description
One, technical field:
The invention belongs to the manufacture field of polymkeric substance, is a kind of rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material that adopts the melt-blending process preparation specifically.
Two, background technology:
Organic-inorganic nanocomposite is described as " novel material of 21st century ".Compare with traditional matrix material,, make nano composite material have to be better than the mechanical property and the thermal characteristics of the conventional matrix material of identical chemical ingredients because nanoparticle brings surface and interfacial effect.At present, report that more clay nanocomposites mainly contains polymeric amide (imide)/polynite, unsaturated polyester/laminated clay, polystyrene/clay, polypropylene/clay, styrene-butadiene rubber(SBR)/clay, carboxy nitrile rubber/clay etc., wherein, clay is mainly polynite.
Polyurethane Thermoplastic Elastomer (TPUR) is a class performance and the macromolecular material that a class special, use range wide of complete processing between rubber and plastics, its molecular structure more complicated, it can be widely used in makes automobile interior trim material, bumper material, sole, coating waterproofing material, floor file material, encapsulating compound and thermoplastic, but raw-material modification of TPUR at present and innovation ability do not develop fully, and use properties and the work-ing life of TPUR are not fully exerted.
Three, summary of the invention:
The object of the present invention is to provide a kind of rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material with higher intensity, excellent thermotolerance and heat-resistant aging and a kind of direct, simple, pollution-free, suitability is wide, the simple preparation method of operating procedure.
For achieving the above object, the technical solution used in the present invention is:
A kind of rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material, its special character is: the composition of raw materials component (by weight) of described nano composite material is:
Polyurethane Thermoplastic Elastomer 100-150 part
Organic rectorite clay 1-10 part
Remover 1-5 part
Above-mentioned raw materials is mixed, adopt melt-blending process can prepare rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material.
Above-mentioned Polyurethane Thermoplastic Elastomer is PAUR elastomerics or polyether(poly)urethane elastomerics.
Above-mentioned organic rectorite clay is the rectorite leng of organic quaternary ammonium salt modification rectorite leng or diamine modification.
Above-mentioned remover is stearic acid or resin acid salt.
The preparation method of a kind of rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material, its special character is: with the fusion on double roll mill of thermoplastic polyurethane elastomer R100-150 part, two roll temperatures are controlled at 120-170 ℃, add remover 1-5 part and organic rectorite clay 1-10 part, behind mixing, the thin-pass 10-30min with sheet under the suitable thickness, granulation promptly obtains nano composite material.
The preparation method of a kind of rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material, its special character is: with polyester type thermoplastic polyurethane elastomer R100-150 part, remover 1-5 part, organic rectorite clay 1-10 part, blend on the high speed kneader, on twin screw extruder, melt extrude then, the front-end temperature of twin screw extruder is 80 ℃-110 ℃, 130 ℃-150 ℃ of stage casing temperature, 145 ℃-170 ℃ of back segment temperature, 80 ℃-100 ℃ of head temperatures can obtain clay nanocomposites with the material granulation of extruding.
The present invention is with respect to prior art, and advantage of the present invention is:
1), that the present invention not only makes the clay rectorite leng can be used for the enhancing of urethane is toughness reinforcing, and can be used to strengthen toughness reinforcing other rubber and plastics.
2), the mechanical property of REC/TPUR increases substantially, REC can make the tensile strength of TPUR high to 57.93Mpa by 37.2MPa society, amplification reaches 55.7%.Along with the raising of content, tear strength also is significantly improved, and can make tear strength bring up to 138.8kN/m by 92.8kN/m in institute's research range, has improved 49%.
3), the frictional behaviour of clay alteration urethane improves a lot, and changes by 2.5 milligrams/1000 and brings up to 1.5 milligrams/1000 and change, and improved 40%.
4), melt-blending process of the present invention neither needs solvent, also is not subjected to the restriction of polymer dissolution, is the most direct, the simplest, pollution-free a kind of, suitability is wide, operating procedure simply prepares organic-inorganic nanocomposite method.
Four, description of drawings:
Fig. 1 adopts mixing roll melt-blending process technological process of production figure for the present invention;
Fig. 2 adopts forcing machine melt-blending process technological process of production figure for the present invention;
Five, embodiment:
Rectorite leng (REC) is a kind of nonmetal mineral reserve with regular interstratified structure, and similar with polynite is a kind of layered silicate, and interlayer has tradable hydrated cation.REC is one of inorganic natural minerals of easily separated one-tenth nano level microplate few in number, through the processing that suitably organises, the REC surface property can improve, and interlamellar spacing can increase, and the rectorite leng after interlamellar spacing increases can carry out the compound preparation intercalated nano-composite of intercalation with polymkeric substance.
Polyurethane Thermoplastic Elastomer (TPUR) is the macromolecular material that a class special, use range wide of a class performance between rubber and plastics.Although TPUR has a lot of advantages and Application Areas, but the raw-material further enhancing modified of TPUR also is a new problem in the macromolecular material research at present, therefore researching and developing clay enhancing TPUR will improve these product performance and have significant values enlarging the Application Areas of TPUR material.
The method for preparing clay nanocomposites is a lot, the polymer melt intercalation compounding had both shown needs solvent, also not being subjected to the restriction of polymer dissolution, is the most direct, the simplest, pollution-free a kind of, suitability is wide, operating procedure simply prepares organic-inorganic nanocomposite novel method.
Referring to Fig. 1, the present invention utilizes this method, with thermoplastic polyurethane elastomer R100-150 part (by weight) fusion on double roll mill, two roll temperatures are controlled at 120-170 ℃, add remover 1-5 part and organic rectorite clay 1-10 part, with sheet under the suitable thickness, granulation promptly obtains the nano composite material of excellent performance behind mixing, the thin-pass 10-30min.Above-mentioned Polyurethane Thermoplastic Elastomer can be PAUR elastomerics or polyether(poly)urethane elastomerics; The organic rectorite clay can be the rectorite leng of organic quaternary ammonium salt modification rectorite leng or diamine modification; And described remover is stearic acid or resin acid salt.Embodiment 1:
With hardness is polyester type thermoplastic polyurethane elastomer R100 part fusion on double roll mill of 85A, two roll temperatures are controlled at 145 ℃, add 2 parts of removers, 8 parts of organic rectorite clays, with sheet under the suitable thickness, granulation promptly obtains nano composite material behind premix, the thin-pass 30min.Embodiment 2
With hardness is polyether-type thermoplastic polyurethane elastomer R100 part fusion on double roll mill of 85A, two roll temperatures are controlled at 120 ℃, add 2 parts of removers, 8 parts of organic rectorite clays, with sheet under the suitable thickness, granulation promptly obtains nano composite material behind premix, the thin-pass 30min.
Referring to Fig. 2, the present invention is with thermoplastic polyurethane elastomer R100-150 part, remover 1-5 part, organic rectorite clay 1-10 part, blend on the high speed kneader, on twin screw extruder, melt extrude then, the front-end temperature of twin screw extruder is 80 ℃-110 ℃, 130 ℃-150 ℃ of stage casing temperature, 145 ℃-170 ℃ of back segment temperature, 80 ℃-100 ℃ of head temperatures can obtain clay nanocomposites with the material granulation of extruding.Embodiment 3
With polyester type thermoplastic polyurethane elastomer R100 part, 2 parts of removers, 8 parts of organic rectorite clays, blend on the high speed kneader melt extrudes on twin screw extruder then, processing parameter: 80 ℃ of front-end temperatures, 130 ℃ of stage casing temperature, 145 ℃ of back segment temperature, 80 ℃ of head temperatures.The material granulation of extruding can be obtained clay nanocomposites.Embodiment 4
With polyether-type thermoplastic polyurethane elastomer R100 part, 2 parts of removers, 8 parts of organic rectorite clays, blend on the high speed kneader melt extrudes on twin screw extruder then, processing parameter: 110 ℃ of front-end temperatures, 150 ℃ of stage casing temperature, 170 ℃ of back segment temperature, 100 ℃ of head temperatures.The material granulation of extruding can be obtained clay nanocomposites.
In the process of preparation nano composite material, different types of organic clay OREC1, OREC2, OREC3 and polyurethane elastomer R1 blend obtain different types of matrix material OREC1/TPUR1, OREC2/TPUR1, OREC3/TPUR1, and it is OREC1/TPUR2 and OREC1/TPUR3 that organic clay OREC1 and TPUR2, TPUR3 blend obtain matrix material.Its performance characterization is as follows:
1, the mechanical property of matrix material
As shown in table 1.As can be seen, the performance of material is greatly improved after organic rectorite and the melt polyurethane blend, the mechanical property difference of the matrix material that different organic rectorites obtains.Different with a kind of organic rectorite with the performance of composites that different polyurethane comixings obtain.In any case but the mechanical property of matrix material all obtains raising by a relatively large margin.
The mechanical property performance prescription OREC1/ OREC2/ OREC3/ OREC1/ of table 1 matrix material
Pure urethane 37.8 37.8 37.8 35.45 MPa of TPUR1 TPUR1 TPUR1 TPUR2 tensile strength fill a prescription 1 53.8 49.27 40.97 41.01
Fill a prescription 2 46.6 43 41.41 38.25
The pure urethane 640 640 640 643. of 3 38.54 33.02 28.0 36.65 elongation at breaks of filling a prescription
% fills a prescription 1 604 608 586 673.
Fill a prescription 2 673 648 597 620
Pure urethane 92.8 92.8 92.8 90.2 KJ/m of 3 529 557 553 594 tear strengths of filling a prescription fill a prescription 1 112.71 99.04 90.99 107.3
Fill a prescription 2 127.6 117.9 103.84 113.5
Fill a prescription 3 137.85 129.83 9 1.07 115.6
2, the thermal characteristics of matrix material
The thermal characteristics of matrix material is as shown in table 2.As can be seen, the Vicat softening point of matrix material changes little, and initial heat decomposition temperature is greatly improved, and maximum weight loss rate obtains reducing.
The hot property composite TPUR1 OREC1/TPUR1 Vicat softening point of the table 2 composite ℃ 70 72 initial heat decomposition temperature ℃ temperature that 347 360 maximum weight loss rates are corresponding ℃ 386.6 415.4 maximum weight loss rate % 79.9 68.9
3, the aging resistance of matrix material
The heat-resisting air aging and the hot oil bath aging resistance of matrix material can see Table shown in 3,4.As can be seen, under the same temperature, under the same time, the heat-resistant air aging property of matrix material is greatly improved, and the property retention rate is higher; Simultaneously, under the room temperature, in the same time, the oil resistance of matrix material is greatly improved.
The heat-resisting air aging of table 3 matrix material (120 ℃ of air themperature)
| ??????????????TPUR1?????????????????????OREC1/TPUR1 ?0h??????24h????48h?????72h?????0h??????24h?????48h?????72h | |
| Tensile strength Mpa strength retention % | 37.4????19.7????19.1????18.8????44.8????26.0????23.2????22.6 ????????52.7????51.1????50.3????????????58??????51.8????50.4 |
Table 4 matrix material oil-proofness (40# machine oil is under the room temperature)
TPUR3???????????????????????????OREC?1/TPUR3
The 0h 24h 72h 168h Oh 24h 72h 168h strong 44.8 39.1 38.0 31.9 44.8 43.44 43.32 35.66 degree Mpa 87.3 84.8 71.2 96.96 96.7 79.6 strength retention % that stretch
4, the electrical property of matrix material
The electrical property of matrix material is shown in table 5..As can be seen, the voltage breakdown of matrix material is improved, and reduces but volume specific resistance is relative with surface resistivity.
The electrical property of table 5 matrix material
ρ
s×??????????????????????ρ
v×???????????????????E(MV/m)
10
12(Ω cm) 10
11(Ω cm) TPUR1 387 176 1.45REC1/TUPR1 3.04 4.2 1.61 annotate: ρ
sBe surface resistivity, ρ
vBe volume resistance, E is a voltage breakdown
Compound polyurethane material after the modification can be widely used in makes automobile interior trim material, bumper material, automobile component material, bearing circle, automobile exterior panel, door-plate, splash pan, sole, coating waterproofing material, floor file material, encapsulating compound and thermoplastic.Polyurethane elastomer behind the clay alteration has more low abrasion, high frictional coefficient and less noise in addition, so can make the transport unit in colliery and mine of it.Can make the gear of toothed gear pump and the wear-resistant liner of various pumps, rotating screen and sieve plate etc. with the urethane of high rigidity.
Claims (6)
1, rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material is characterized in that: the composition of raw materials component (by weight) of described nano composite material is:
Polyurethane Thermoplastic Elastomer 100-150 part
Organic rectorite clay 1-10 part
Remover 1-5 part
Above-mentioned raw materials is mixed, adopt melt-blending process can prepare rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material.
2, rectorite leng according to claim 1/Polyurethane Thermoplastic Elastomer nano composite material is characterized in that: described Polyurethane Thermoplastic Elastomer is PAUR elastomerics or polyether(poly)urethane elastomerics.
3, rectorite leng according to claim 1 and 2/Polyurethane Thermoplastic Elastomer nano composite material is characterized in that: described organic rectorite clay is the rectorite leng of organic quaternary ammonium salt modification rectorite leng or diamine modification.
4, rectorite leng according to claim 3/Polyurethane Thermoplastic Elastomer nano composite material is characterized in that: described remover is stearic acid or resin acid salt.
5, the preparation method of rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material is characterized in that:
With the fusion on double roll mill of thermoplastic polyurethane elastomer R100-150 part, two roll temperatures are controlled at 120-170 ℃, add remover 1-5 part and organic rectorite clay 1-10 part, behind mixing, the thin-pass 10-30min with sheet under the suitable thickness, granulation promptly obtains nano composite material.
6, the preparation method of rectorite leng/Polyurethane Thermoplastic Elastomer nano composite material is characterized in that:
With polyester type thermoplastic polyurethane elastomer R100-150 part, remover 1-5 part, organic rectorite clay 1-10 part, blend on the high speed kneader melt extrudes on twin screw extruder then, and the front-end temperature of twin screw extruder is 80 ℃-110 ℃, 130 ℃-150 ℃ of stage casing temperature, 145 ℃-170 ℃ of back segment temperature, 80 ℃-100 ℃ of head temperatures can obtain clay nanocomposites with the material granulation of extruding.
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| CN 02139341 CN1200973C (en) | 2002-08-08 | 2002-08-08 | Rectorite/thermoplastic polyurethane elastomer nano composite material and preparing method |
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| CN 02139341 CN1200973C (en) | 2002-08-08 | 2002-08-08 | Rectorite/thermoplastic polyurethane elastomer nano composite material and preparing method |
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| CN1200973C CN1200973C (en) | 2005-05-11 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101374766B (en) * | 2006-01-31 | 2012-07-18 | 独立行政法人产业技术综合研究所 | Clay film and method for producing same |
| WO2021077448A1 (en) * | 2019-10-22 | 2021-04-29 | 江苏中路工程技术研究院有限公司 | New and old pavement base course joining interface treatment material and preparation method therefor |
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2002
- 2002-08-08 CN CN 02139341 patent/CN1200973C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101374766B (en) * | 2006-01-31 | 2012-07-18 | 独立行政法人产业技术综合研究所 | Clay film and method for producing same |
| WO2021077448A1 (en) * | 2019-10-22 | 2021-04-29 | 江苏中路工程技术研究院有限公司 | New and old pavement base course joining interface treatment material and preparation method therefor |
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