CN1059685C - Polyurethane-containing thermoplastic ternary composition - Google Patents
Polyurethane-containing thermoplastic ternary composition Download PDFInfo
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- CN1059685C CN1059685C CN96116471A CN96116471A CN1059685C CN 1059685 C CN1059685 C CN 1059685C CN 96116471 A CN96116471 A CN 96116471A CN 96116471 A CN96116471 A CN 96116471A CN 1059685 C CN1059685 C CN 1059685C
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Abstract
The present invention relates to a polyurethane-containing thermoplastic ternary composition containing 40 to 90 wt% of random copolymer of styrene and acrylonitrile, 5 to 30 wt% of thermoplastic polyurethane and 5 to 50 wt% of copolymer of ethene and vinyl acetate. The composition has the characteristics of good aging resistant performance, simple production process and low production cost. The mechanical performance of the composition is equivalent to that of universal stage ABS. The composition which is novel toughened plastic can be used in plastic industry.
Description
The present invention relates to toughened plastics, particularly about containing the ternary toughened plastics of urethane.
Well-known ABS plastic is typical rubber toughened plastics.It has good comprehensive mechanical properties, and easily machine-shaping is that present consumption is big, uses universal widely engineering plastics.Yet because divinyl contains two keys in the ABS component, easily oxidative degradation under action of ultraviolet radiation, weathering resistance is relatively poor, outdoor exposure after half a year shock strength will descend 45%.Owing to the great disparity of refractive index between plastics phase and the rubber phase, resin transparent is poor, has limited its application in some aspects in addition.Improve the ABS aspect of performance how, people have done a large amount of work from modification by copolymerization and blending and modifying aspect for this reason.Document clear 57～34146 has reported that random copolymers (being called for short SAN) and the thermoplastic polyurethane (being called for short TPU) with styrene-acrylonitrile is feedstock production transparency thermoplastic resin composition.This patent mainly is to be to use the urethane of polyester type to be raw material, by the coupling of two raw material refractive index, obtains a kind of toughened plastics of the transparency.But the mechanical property of its toughening compositions is not ideal enough, uses a large amount of thermoplastic polyurethanes simultaneously, and the cost of its raw material is also higher.In order to overcome the shortcoming that above-mentioned technology exists, a kind of mechanical properties such as good yield strength, breaking tenacity and elongation at break that have are provided, the also cheaper toughened plastics of while raw materials cost, the inventor has invented the thermoplastic ternary composition that contains urethane.
The objective of the invention is to realize by following technical scheme: a kind of thermoplastic ternary composition that contains urethane contains the multipolymer of ethylene-vinyl acetate of thermoplastic polyurethane and 5～50% (weight) of random copolymers and 5～30% (weight) of the styrene-acrylonitrile of 40～90% (weight).
In the technique scheme in the styrene-acrylonitrile random copolymers content of vinyl cyanide be 15～40% (weight), its preferable range is 20～30% (weight).The percentage composition preferable range of styrene-acrylonitrile random copolymers is 60～80% (weight) in the composition.Thermoplastic polyurethane percentage composition preferable range is 5～20% (weight), and ethylene-vinyl acetate copolymer percentage composition preferable range is 10～30% (weight).Used thermoplastic polyurethane is to constitute hard section by the vulcabond of 15～50% (weight) and chainextender, and the polyethers of 50～85% (weight), polyester or polyether-polyester constitute soft section.Wherein thermoplastic polyurethane is by the vulcabond and the hard section of chainextender formation of 20～30% (weight) preferably, and the polyethers of 70～80% (weight), polyester or polyether-polyester constitute soft section.
Used Polyurethane Thermoplastic Elastomer among the present invention, it is oligomer polyol and vulcabond and chainextender small molecules glycol or diamines such as multipolymer by polyester, polyethers or polyester and polyethers, makes by soft, the hard section segmented copolymer of alternately forming by addition polymerization progressively.Wherein polyester polyol can be formed by the dibasic alcohol polycondensation of different saturated fatty acids or aromatic acid and different varieties.
The preparation of the present composition can be extruded with twin-screw extruder, static mixer or twin screw.Blending temperature is 160～190 ℃, and the blend time is 5～10 minutes.The test of sample mechanical property is: the blend that above-mentioned technology blend is made is at 160～180 ℃, 60Kg/cm earlier
2Vulcanizing press in be molded into thin slice about 1mm, cut into inferior bell strip then, on DL-1000 type electronic tensile machine, measure the stress～strain curve of sample, draw speed 5mm/min.Calculate yield strength, breaking tenacity and the elongation at break of composition thus.
In the technical program, because with the saturated high brittle plastic blend just that contains the polar thermoplastic elastomer and be complementary with it, by regulating the chemical structure and the composition of thermoplastic elastomer, make the special interaction of having set up appropriateness between rubber phase and the plastics phase, thermoplastic elastomer plays dual parts toughness reinforcing and increase-volume simultaneously.Use the multipolymer instead of part polyurethane component of ethylene-vinyl acetate simultaneously, both kept the mechanical property of composition, reduced raw materials cost simultaneously.By simple mechanical blending, need not add phase solvent at last, contain urethane ternary toughened plastics with regard to a new generation that has obtained having favorable comprehensive mechanical property.The yield strength of composition, mechanical properties such as breaking tenacity and elongation at break are equivalent to the index of general purpose grade ABS resin.In addition, because need not double bond containing polybutadiene rubber, make thermoplastic compounds have aging resistance preferably, obtained effect preferably.
[embodiment 1]
Random copolymers with 80 gram styrene-acrylonitriles, wherein acrylonitrile content is 15% (weight), 60 gram polyester type thermoplastic polyurethanes, wherein diisocyanate content is that 15% (weight), 60 multipolymers that restrain ethylene-vinyl acetates are put into the twin-screw extruder blend, blending temperature is 170 ℃, 15 minutes time.After blend finishes, with the blend that makes at 170 ℃, 60Kg/cm
2Vulcanizing press in be molded into thin slice about 1mm, cut into the dumbbell strip then, on DL-1000 type electronic tensile machine, measure the stress～strain curve of sample, draw speed is 5mm/min.Calculating yielding stress thus is 26.5MPa, and breaking tenacity is 34.5MPa, and elongation at break is 275%.[embodiment 2]
Test method and test method of calculation according to embodiment 1.Random copolymers 100 grams that add styrene-acrylonitrile, wherein acrylonitrile content is 15% (weight), 80 gram polyether-type thermoplastic polyurethanes, wherein diisocyanate content is the multipolymer of 15% (weight), 20 gram ethylene-vinyl acetates.Calculation result after tested: yielding stress is 24.8MPa, and breaking tenacity is 37.1MPa-, and elongation at break is 285.6%.[embodiment 3]
Test method and test method of calculation according to embodiment 1.Random copolymers 120 grams that add styrene-acrylonitrile, wherein acrylonitrile content is the thermoplastic polyurethane of 20% (weight), 44 gram polyether-polyester types, wherein diisocyanate content is the multipolymer of 20% (weight), 36 gram ethylene-vinyl acetates.Calculation result after tested: yielding stress is 34.5MPa, and breaking tenacity is 31.8MPa, and elongation at break is 102.3%.[embodiment 4]
Test method and test method of calculation according to embodiment 1.Random copolymers 120 grams that add styrene-acrylonitrile, wherein acrylonitrile content is 30% (weight), 56 gram polyester type thermoplastic polyurethanes, wherein diisocyanate content is the multipolymer of 25% (weight), 24 gram ethylene-vinyl acetates.Calculation result after tested: yielding stress is 32.9MPa, and breaking tenacity is 32.4MPa, and elongation at break is 153.2%.[embodiment 5]
Test method and test method of calculation according to embodiment 1.Random copolymers 140 grams that add styrene-acrylonitrile, wherein acrylonitrile content is the thermoplastic polyurethane of 25% (weight), 32 gram polyether-polyester types, wherein diisocyanate content is the multipolymer of 30% (weight), 28 gram ethylene-vinyl acetates.Calculation result after tested: yielding stress is 39.8MPa, and breaking tenacity is 32.5MPa, and elongation at break is 37.2%.[embodiment 6]
Test method and test method of calculation according to embodiment 1.Random copolymers 140 grams that add styrene-acrylonitrile, wherein acrylonitrile content is 20% (weight), 40 gram polyether-type thermoplastic polyurethanes, wherein diisocyanate content is the multipolymer of 25% (weight), 20 gram ethylene-vinyl acetates.Calculation result after tested: yielding stress is 39.4MPa, and breaking tenacity is 31.0MPa, and elongation at break is 60.3%.[embodiment 7]
Test method and test method of calculation according to embodiment 1.Random copolymers 160 grams that add styrene-acrylonitrile, wherein acrylonitrile content is 15% (weight), 8 gram polyester type thermoplastic polyurethanes, wherein diisocyanate content is the multipolymer of 20% (weight), 32 gram ethylene-vinyl acetates.Calculation result after tested: yielding stress is 41.7MPa, and breaking tenacity is 38.1MPa, and elongation at break is 9.4%.[embodiment 8]
Test method and test method of calculation according to embodiment 1, random copolymers 180 grams that add styrene-acrylonitrile, wherein acrylonitrile content is 40% (weight), 10 gram polyether-type thermoplastic polyurethanes, and wherein diisocyanate content is the multipolymer of 40% (weight), 10 gram ethylene-vinyl acetates.Calculation result after tested: yielding stress is 59.8MPa, and breaking tenacity is 52.6MPa, and elongation at break is 8.9%." comparative example 1 "
200 gram general purpose grade ABS resin are put into twin-screw extruder, and 170 ℃ of heating resin Da Wendu are then at 170 ℃ of temperature, pressure 60Kg/cm
2Vulcanizing press in ABS resin is molded into thin slice about 1mm, cut into the dumbbell strip then, on DL-1000 type electronic tensile machine, measure the stress～strain allusion quotation line of sample, draw speed is 5m/m.Calculating yielding stress thus is 40MPa, and breaking tenacity is 32MPa, and elongation at break is 40%.
Claims (8)
1. thermoplastic ternary composition that contains urethane, the thermoplastic polyurethane of random copolymers and 5～30% (weight) that contains the styrene-acrylonitrile of 40～90% (weight) is characterized in that also containing in the composition multipolymer of the ethylene-vinyl acetate of 5～50% (weight).
2. according to the described thermoplastic ternary composition that contains urethane of claim 1, the content that it is characterized in that vinyl cyanide in the styrene-acrylonitrile random copolymers is 15～40% (weight).
3. according to the described thermoplastic ternary composition that contains urethane of claim 2, the content that it is characterized in that vinyl cyanide in the styrene-acrylonitrile random copolymers is 20～30% (weight).
4. according to the described thermoplastic ternary composition that contains urethane of claim 1, the percentage composition that it is characterized in that styrene-acrylonitrile random copolymers in the composition is 60～80% (weight).
5. according to the described thermoplastic ternary composition that contains urethane of claim 1, the percentage composition that it is characterized in that thermoplastic polyurethane in the composition is 5～20% (weight).
6. according to the described thermoplastic ternary composition that contains urethane of claim 1, it is characterized in that thermoplastic polyurethane is by the vulcabond and the hard section of chainextender formation of 15～50% (weight) in the composition, the polyethers of 50～85% (weight), polyester or polyether-polyester constitute soft section.
7. according to the described thermoplastic ternary composition that contains urethane of claim 6, it is characterized in that thermoplastic polyurethane is by the vulcabond and the hard section of chainextender formation of 20～30% (weight) in the composition, the polyethers of 70～80% (weight), polyester or polyether-polyester constitute soft section.
8. according to the described thermoplastic ternary composition that contains urethane of claim 1, the percentage composition that it is characterized in that ethylene-vinyl acetate copolymer in the composition is 10～30% (weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116471A CN1059685C (en) | 1996-08-20 | 1996-08-20 | Polyurethane-containing thermoplastic ternary composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116471A CN1059685C (en) | 1996-08-20 | 1996-08-20 | Polyurethane-containing thermoplastic ternary composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1174211A CN1174211A (en) | 1998-02-25 |
| CN1059685C true CN1059685C (en) | 2000-12-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116471A Expired - Fee Related CN1059685C (en) | 1996-08-20 | 1996-08-20 | Polyurethane-containing thermoplastic ternary composition |
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| Country | Link |
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| CN (1) | CN1059685C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI396718B (en) * | 2007-03-15 | 2013-05-21 | Dainippon Ink & Chemicals | Humid hardening type urethane composition for water-proofing material and urethane water-proofing material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5059243A (en) * | 1973-09-22 | 1975-05-22 | ||
| JPS5734146A (en) * | 1980-08-11 | 1982-02-24 | Asahi Chem Ind Co Ltd | Transparent impact-resistant thermoplastic resin composition |
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1996
- 1996-08-20 CN CN96116471A patent/CN1059685C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5059243A (en) * | 1973-09-22 | 1975-05-22 | ||
| JPS5734146A (en) * | 1980-08-11 | 1982-02-24 | Asahi Chem Ind Co Ltd | Transparent impact-resistant thermoplastic resin composition |
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| Publication number | Publication date |
|---|---|
| CN1174211A (en) | 1998-02-25 |
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