CN101302332B - Carbon dioxide-cyclohexene oxide copolymer brittlement modified method - Google Patents
Carbon dioxide-cyclohexene oxide copolymer brittlement modified method Download PDFInfo
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- CN101302332B CN101302332B CN200710022237XA CN200710022237A CN101302332B CN 101302332 B CN101302332 B CN 101302332B CN 200710022237X A CN200710022237X A CN 200710022237XA CN 200710022237 A CN200710022237 A CN 200710022237A CN 101302332 B CN101302332 B CN 101302332B
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Abstract
The invention provides a method for modifying the brittleness of carbon dioxide-cyclohexene oxide copolymers. The method comprises the following steps of: taking 40 to 90 portions of carbon dioxide-cyclohexene oxide copolymers, 8 to 48 portions of elastic elements, and 2 to 12 portions of terpolymers of acrylonitrile-styrene-acrylic acid, according to weight portion; uniformly mixing the carbon dioxide-cyclohexene oxide copolymers, the elastic elements and the terpolymers of acrylonitrile-styrene-acrylic acid in solvent, or in a Banbury mixer or in a double-screw extruder; and drying the mixture to acquire blends with improved brittleness. The method improves the brittleness of the carbon dioxide-cyclohexene oxide copolymers, maintains the tensile-strength over 30 MPa, improves the elongation even up to over multiple times, and maintains a high vitrification temperature of PCHC.
Description
Technical field
The present invention relates to field of polymer technology, be specifically related to a kind of method of carbonic acid gas-cyclohexene oxide copolymer being carried out modification.
Background technology
Carbonic acid gas-cyclohexene oxide copolymer (PCHC) is by carbonic acid gas-cyclohexene oxide copolymerization synthetic aliphatic polycarbonate.Compare with in bisphenol A polycarbonate, aliphatic polycarbonate is greenhouse gases---the carbonic acid gas that in a large number environment worked the mischief of simply nontoxic, the effective utilization of synthesis technique not only, and have biodegradability, and can not cause white pollution, have good economy, society and environmental benefit.But general aliphatic polycarbonate is because second-order transition temperature is lower, near room temperature, has limited their application as engineering plastics greatly, and only can be applied to fields such as coating, tackiness agent, elastomerics and low temperature oxygen barrier film.Carbonic acid gas-cyclohexene oxide copolymer has possessed high glass transition (116 ℃), and application prospect is more wide.But this polymkeric substance but present brittle shortcoming (referring to Journal ofApplied Polymer Science, 2003, Vol.89,1163-1176 and Polymer, 2001,42,3995-4004).Acrylonitrile-butadiene-styrene terpolymer (ABS) and analogue have superpower workability, appearance characteristics, and resistance to impact shock and price that low creep properties and excellent size are stable and very high are lower.
Summary of the invention
The objective of the invention is to improve the mechanical property of carbonic acid gas-cyclohexene oxide copolymer, a kind of thermomechanical property that both keeps PCHC preferably is provided, also improve its toughness, keep the method for modifying of its biodegradability simultaneously.
Purpose of the present invention can reach by following measure:
A kind of brittlement modified method of carbonic acid gas-cyclohexene oxide copolymer, get 40～90 parts of carbonic acid gas-cyclohexene oxide copolymers (PCHC) by weight, 8～48 parts of elastic components, 2～12 parts of acrylonitrile-styrenes-acrylic acid terpolymer (AS5M), they are mixed in solvent or in Banbury mixer or in twin screw extruder, obtain the blend that fragility is improved.
In each raw material, preferred 60～90 parts of carbonic acid gas-cyclohexene oxide copolymer, 70～80 parts of the bests; Preferred 8～30 parts of elastic component, 20～30 parts of the bests; Preferred 5～10 parts of acrylonitrile-styrene-acrylic acid terpolymer, 10 parts of the bests.
Carbonic acid gas-cyclohexene oxide copolymer is the structure that meets following formula:
Wherein: n:(n+m)=0.80～100.PCHC used in the present invention can be according to Chinese patent CN1116332C and CN1094945C preparation.
Described elastic component is an ABS (vinyl cyanide, divinyl and cinnamic random copolymers, the ABST100 of toray), SBS (vinylbenzene, the segmented copolymer of divinyl), SIS (vinylbenzene and isoprene block copolymer) or SEBS (vinylbenzene, ethene and butadiene block copolymer), the ABS T100 of wherein preferred toray.
Ratio between the described acrylonitrile-styrene-acrylic acid terpolymer, three kinds of compositions is 40:50:5, molecular weight 3-10 ten thousand.
The employing solvent method mixes, and solvent is selected from chloroform, tetrahydrofuran (THF), N, one or more in dinethylformamide, N-Methyl pyrrolidone, toluene or the dimethylbenzene; Boiling off behind the solvent mixture can vacuum-drying, and drying temperature is 40～100 ℃, 6～15 hours time, 10 hours the bests; Preferred blanketing with inert gas between mixing period.
When each raw material mixed with Banbury mixer or twin screw extruder, the temperature of Banbury mixer or twin screw extruder was 170～220 ℃, and the speed of Banbury mixer is 30～200r/min; Before entering Banbury mixer or twin screw extruder, mixture can vacuum-drying, and drying temperature is 40～100 ℃, 6～15 hours time, 10 hours the bests.
The modified blends of gained of the present invention is made the film stretching batten, the test tensile property.Test result shows, method of modifying of the present invention has improved the fragility of carbonic acid gas-cyclohexene oxide copolymer, and tensile strength remains on more than the 30MPa, elongation at break increases even can also keep the high glass transition temperature of PCHC simultaneously to more than the several times.
Embodiment
Embodiment 1
Get PCHC (weight-average molecular weight 230,000, molecular weight distribution 3.5, n:(n+m)=0.9) 80g (weight part, down with), ABS10g, acrylonitrile-styrene-acrylic acid terpolymer AS5M10g.Mix the back in 80 ℃ of following vacuum-dryings 10 hours.In the Haake Banbury mixer, obtain the blend of PCHC and ABS 200 ℃ of following banburyings with the speed of 30r/min.
Above-mentioned blend is made the film stretching batten, the test tensile property.Young's modulus is 1.8GPa, and tensile strength is 41.4MPa, elongation at break 3.3%, and second-order transition temperature is 119 ℃.
Embodiment 2
Get PCHC (weight-average molecular weight 230; 000; molecular weight distribution 2.5; n:(n+m)=0.95) PCHC80g; ABS10g, acrylonitrile-styrene-acrylic acid terpolymer AS5M10g is dissolved under nitrogen protection in the 50ml chloroform; most of chloroform is removed in underpressure distillation, mixes the back in 80 ℃ of following vacuum-dryings 10 hours.
Above-mentioned blend is made the film stretching batten, the test tensile property.Young's modulus is 1.4GPa, and tensile strength is 42MPa, elongation at break 8.7%, and second-order transition temperature is 111.3 ℃.
Embodiment 3
Get PCHC (weight-average molecular weight 190,000, molecular weight distribution 2.5, n:(n+m)=0.86) 70g, ABS20g, acrylonitrile-styrene-acrylic acid terpolymer AS5M10g.Mix the back in 80 ℃ of following vacuum-dryings 10 hours.In twin screw extruder, obtain the blend of PCHC and ABS 200 ℃ of following banburyings with the speed of 30r/min.
Above-mentioned blend is made the film stretching batten, the test tensile property.Young's modulus is 1.3GPa, and tensile strength is 33.3MPa, elongation at break 4.0%, and second-order transition temperature is 121 ℃.
Embodiment 4
Get PCHC (weight-average molecular weight 190; 000; molecular weight distribution 2.5; n:(n+m)=0.86) 75g; ABS15g, acrylonitrile-styrene-acrylic acid terpolymer AS5M10g is dissolved under nitrogen protection in the 50ml chloroform; most of chloroform is removed in underpressure distillation, mixes the back in 80 ℃ of following vacuum-dryings 10 hours.
Above-mentioned blend is made the film stretching batten, the test tensile property.Young's modulus is 1.4GPa, and tensile strength is 36.7MPa, elongation at break 12%, and second-order transition temperature is 108.8 ℃.
Embodiment 5
Get PCHC (weight-average molecular weight 190,000, molecular weight distribution 2.5, n:(n+m)=0.80) 60g, ABS30g, acrylonitrile-styrene-acrylic acid terpolymer AS5M10g.Mix the back in 80 ℃ of following vacuum-dryings 10 hours.In the Haake Banbury mixer, obtain the blend of PCHC and ABS 200 ℃ of following banburyings with the speed of 30r/min.
Above-mentioned blend is made the film stretching batten, the test mechanical property.Young's modulus is 1.3GPa, and tensile strength is 32MPa, elongation at break 5.6%, and second-order transition temperature is 121 ℃.
Embodiment 6
Get PCHC (weight-average molecular weight 190; 000; molecular weight distribution 2.5; n:(n+m)=0.98) 70g; ABS20g, acrylonitrile-styrene-acrylic acid terpolymer AS5M10g is dissolved under nitrogen protection in the 50ml chloroform; most of chloroform is removed in underpressure distillation, mixes the back in 80 ℃ of following vacuum-dryings 10 hours.
Above-mentioned blend is made the film stretching batten, the test tensile property.Young's modulus is 1.5GPa, and tensile strength is 36.8MPa, elongation at break 15%, and second-order transition temperature is 117.6 ℃.
Embodiment 7
Get PCHC (weight-average molecular weight 250,000, molecular weight distribution 4.5, n:(n+m)=0.99) 60g, SBS40g, acrylonitrile-styrene-acrylic acid terpolymer AS5M4g.Mix the back in 70 ℃ of following vacuum-dryings 15 hours.In twin screw extruder, obtain the blend of PCHC and SBS 190 ℃ of following banburyings with the speed of 60r/min.
Above-mentioned blend is made the film stretching batten, the test mechanical property.Young's modulus is 1.4GPa, and tensile strength is 32MPa, elongation at break 5.6%, and second-order transition temperature is 121 ℃.
Embodiment 8
Get PCHC (weight-average molecular weight 250,000, molecular weight distribution 4.5, n:(n+m)=0.99) 60g, SIS20g, acrylonitrile-styrene-acrylic acid terpolymer AS5M10g.Mix the back in 70 ℃ of following vacuum-dryings 15 hours.In twin screw extruder, obtain the blend of PCHC and SIS 180 ℃ of following banburyings with the speed of 150r/min.
Above-mentioned blend is made the film stretching batten, the test mechanical property.Young's modulus is 1.3GPa, and tensile strength is 34MPa, elongation at break 6%, and second-order transition temperature is 120 ℃.
Embodiment 9
Get PCHC (weight-average molecular weight 250; 000; molecular weight distribution 4.5; n:(n+m)=0.99) 80g; SEBS20g, acrylonitrile-styrene-acrylic acid terpolymer AS5M10g is dissolved under nitrogen protection in the 50ml tetrahydrofuran (THF); most of tetrahydrofuran (THF) is removed in underpressure distillation, mixes the back in 90 ℃ of following vacuum-dryings 8 hours.
Above-mentioned blend is made the film stretching batten, the test tensile property.Young's modulus is 1.4GPa, and tensile strength is 36.9MPa, elongation at break 15%, and second-order transition temperature is 118 ℃.
Embodiment 10
Get PCHC (weight-average molecular weight 250; 000; molecular weight distribution 4.5; n:(n+m)=0.99) 80g; ABS30g; acrylonitrile-styrene-acrylic acid terpolymer AS5M10g is dissolved under nitrogen protection in the 50ml toluene, and most of toluene is removed in underpressure distillation, mixes the back in 100 ℃ of following vacuum-dryings 6 hours.
Above-mentioned blend is made the film stretching batten, the test tensile property.Young's modulus is 1.5GPa, and tensile strength is 36.6MPa, elongation at break 13%, and second-order transition temperature is 116 ℃.
Comparative example 1
Get PCHC (weight-average molecular weight 190,000, molecular weight distribution 2.5, n:(n+m)=0.80) in 80 ℃ of following vacuum-dryings 10 hours, speed with 30r/min in the Haake Banbury mixer obtains PCHC 200 ℃ of following banburyings, and above-mentioned PCHC is made the film stretching batten, the test tensile property.Young's modulus is 2.2GPa, and tensile strength is 38.3MPa, elongation at break 2.3%, and second-order transition temperature is 106.9 ℃.
Comparative example 2
Get PCHC (weight-average molecular weight 190,000, molecular weight distribution 2.5, n:(n+m)=0.98), melt under nitrogen protection in the 50ml chloroform, most of chloroform is removed in underpressure distillation, mixes the back in 80 ℃ of following vacuum-dryings 10 hours.Make the film stretching batten after the drying, the test tensile property.Young's modulus is 1.8GPa, and tensile strength is 41.4MPa, elongation at break 3.3%, and second-order transition temperature is 106.9 ℃.
Preparation of film stretching batten and testing method are as follows
With sample on thermocompressor with 200 ℃, be pressed into long 30 millimeters, wide 10 millimeters under 15 MPas, the thin slice that thickness is 0.3 ± 0.05 millimeter, speed with 10 mm/min stretches on film drawer under 23 ℃, records tensile strength and elongation at break, and each batten is surveyed five and averaged.
Claims (5)
1. the brittlement modified method of a carbon dioxide-cyclohexene oxide copolymer, it is characterized in that getting by weight 40～90 parts of carbon dioxide-cyclohexene oxide copolymers, 8～48 parts of elastic components, 2～12 parts of acrylonitrile-styrenes-acrylic acid terpolymer, they are mixed in solvent or in Banbury mixer or in twin screw extruder, obtain the blend that fragility is improved; Wherein said elastic component is a vinyl cyanide, divinyl and cinnamic random copolymers, vinylbenzene, the segmented copolymer of divinyl, vinylbenzene and isoprene block copolymer or vinylbenzene, ethene and butadiene block copolymer.
2. brittlement modified method according to claim 1, the weight part that it is characterized in that described each raw material are 60～90 parts of carbon dioxide-cyclohexene oxide copolymers, 8～30 parts of elastic components, 5～10 parts of acrylonitrile-styrenes-acrylic acid terpolymer.
3. brittlement modified method according to claim 1 and 2 is characterized in that described carbon dioxide-cyclohexene oxide copolymer is the structure that meets following formula:
Wherein: n:(n+m)=0.80～1.
4. brittlement modified method according to claim 1 is characterized in that described solvent is selected from chloroform, tetrahydrofuran (THF), N, one or more in dinethylformamide, N-Methyl pyrrolidone, toluene or the dimethylbenzene.
5. brittlement modified method according to claim 1, when it is characterized in that each raw material mixes with Banbury mixer or twin screw extruder, the temperature of Banbury mixer or twin screw extruder is 170～220 ℃, the speed of Banbury mixer is 30～200r/min.
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| CN106243312B (en) * | 2016-08-25 | 2019-05-10 | 广东达志环保科技股份有限公司 | A kind of preparation method of the polycarbonate waterborne polyurethane lotion of ultrahigh hardness |
| CN112094490B (en) * | 2020-09-28 | 2021-09-21 | 中国科学院长春应用化学研究所 | Carbon dioxide-cyclohexene oxide copolymer composite material and preparation method thereof |
| CN112646345B (en) * | 2020-12-25 | 2021-09-21 | 中国科学院长春应用化学研究所 | High-impact carbon dioxide copolymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110695A (en) * | 1994-01-12 | 1995-10-25 | 通用电气公司 | Impact resistant resin composition |
| CN1814647A (en) * | 2006-03-06 | 2006-08-09 | 浙江大学 | Method for preparing high-molecular-weight polycarbonate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110695A (en) * | 1994-01-12 | 1995-10-25 | 通用电气公司 | Impact resistant resin composition |
| CN1814647A (en) * | 2006-03-06 | 2006-08-09 | 浙江大学 | Method for preparing high-molecular-weight polycarbonate |
Non-Patent Citations (4)
| Title |
|---|
| C.Koning et al.Synthesis and physical characterization of poly(cyclohexane carbonate),synthesized from CO2 and cyclohexene oxide.《Polymer》.2001,第42卷3995-4004. * |
| C.Koningetal.Synthesisandphysicalcharacterizationofpoly(cyclohexanecarbonate) synthesized from CO2 and cyclohexene oxide.《Polymer》.2001 |
| 叶晓光等.脂肪族聚碳酸酯——二氧化碳共聚物的性能及应用.《化学通报》.1997,(第10期),29-34. * |
| 杨淑英等.CO2共聚物新材料研究进展.《化工进展》.1998,(第2期),51-53. * |
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