CN104212166A - Degradable material for signal line and preparation method of degradable material - Google Patents
Degradable material for signal line and preparation method of degradable material Download PDFInfo
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- CN104212166A CN104212166A CN201410452039.7A CN201410452039A CN104212166A CN 104212166 A CN104212166 A CN 104212166A CN 201410452039 A CN201410452039 A CN 201410452039A CN 104212166 A CN104212166 A CN 104212166A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/018—Additives for biodegradable polymeric composition
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a degradable material for a signal line. The degradable material is prepared from the following components in parts by weight: 50-60 parts of degradable polyamide, 30-40 parts of polytetrahydrofuran ether, 8-10 parts of chitin, 10-20 parts of styrene-maleic anhydride copolymer, 3-5 parts of fluorinated silicone rubber and 10-20 parts of nano calcium sulfate, wherein the degradable polyamide is formed by virtue of condensation polymerization of carboxyl-terminated saturated polyester and diamine; and the carboxyl-terminated saturated polyester is formed by virtue of condensation polymerization of alkylene polycarbonate-polylactic acid block copolymer diol, m-phthalic acid and stannous octoate. The invention further discloses a preparation method of the degradable material. The preparation method comprises the steps of preparing raw materials, weighing the raw materials, mixing and squeezing the raw materials, pelletizing and packaging, and the like. The degradable material contains a degradable molecular chain segment and integrates the advantages of thermoplastic polyamide resin, so that the product has the characteristics of degradability, excellent toughness and softness, chemical resistance, abrasive resistance, antibacterial performance, heat resistance, a smooth surface, and the like, and is suitable for manufacturing signal lines such as a headset line.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of signal wire degradation material and preparation method thereof.
Background technology
Signal wire rod in the market updates rapidly, its material characteristics and changes of function also emerge in an endless stream, the plastic material great majority being suitable for signal wire rod more focus on the excellent performance etc. of product, existing most of plastic material is because of difficulties of substantially can not degrading or degrade such as its constructional features, and this type of product production is large, volume is little, recovery is difficult, after discarded, easily cause environmental pollution.
Polyamide thermoplastic resilient material is because of features such as its workability, rubber and plastic characteristic, toughness, and simultaneously the designability of its molecular structure is strong, selects different molecule segments to design its hard section, the structure of soft section, makes it meet the application of different occasion.
But existing most of thermoplastic plastic's material, all can not degrade; And existing a lot of degradable plastics, its snappiness is all poor, is not suitable for again manufacturing signal wire rod.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide the signal wire degradation material of the advantages such as a kind of biodegradable, excellent toughness, softness, chemical-resistant, germ resistance, product surface are smooth.
The present invention also aims to the industrialized process for preparing that above-mentioned signal wire degradation material is provided.
Above-mentioned purpose of the present invention is achieved by the following technical solution:
A kind of signal wire degradation material, it is made up of the component of following parts by weight:
Wherein, described degradable poly acid amides is prepared from by end carboxyl saturated polyester, diamine polycondensation, and wherein said end carboxyl saturated polyester is made up of polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, m-phthalic acid, stannous octoate polycondensation.
The molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000 ~ 10000g/mol, polymerized thylene carbonate alkane ester is wherein one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and poly(lactic acid) is one or both the mixing in L-type poly(lactic acid), D type poly(lactic acid); Polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol causes rac-Lactide ring opening copolymer by polymerized thylene carbonate alkane esterdiol and obtains under the effect of catalyzer, and the method is maturation method, can referenced patent ZL200910155893.6.
In described styrene-maleic anhydride copolymer, the mol ratio of vinylbenzene and maleic anhydride is 2:1, is be prepared from through solution polymerization, biodegradable.
The deacetylation degree of described chitin is 75%.
A preparation method for described signal wire degradation material, it comprises the steps:
(1) degradable poly acid amides is prepared:
(11) be, polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of m-phthalic acid 1.1-1.3 takes raw material, add in reactor, 100 DEG C, vacuum hydro-extraction under 0.01Mpa, add the stannous octoate of the 0.5-1% of system material total amount afterwards, be warmed up to 200 DEG C, melt polycondensation reaction 4-6 hour, lower the temperature 100 DEG C and vacuumize 0.03Mpa, to without overhead product, obtain end carboxyl saturated polyester.
(12), end carboxyl saturated polyester 1 according to mol ratio is step (11) gained: hexamethylene-diamine 1 takes raw material, afterwards agitator is being housed, condenser, nitrogen feed pipe, pressure-regulator, drip in the reactor of tank, first add end carboxyl saturated polyester, after nitrogen purge, be heated to 180 DEG C and treat material melts, through dripping tank instillation hexamethylene-diamine, drip continuously completely under agitation 3 hours, simultaneously gradually continuous warming to reactor temperature to 250 DEG C, the moisture that period reaction produces is discharged through condenser, after hexamethylene-diamine drips, continue stirring 30 minutes at ambient pressure, heat up with speed 0.2 DEG C/min and fix hexamethylene-diamine, pass into steam afterwards and make gas phase portion pressure remain on 0.3Mpa, at temperature keeps 255 DEG C, draw off polymeric amide, cooling, packaging.
(2) raw material is taken in following ratio:
(3) all added in high speed mixer by material and mix, pour in twin screw extruder by gained mixture, controlled working temperature 170-260 DEG C, through mixing extrusion, cooling and dicing, obtains product, packaging.
Wherein, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000-10000g/mol, under the effect of catalyzer, cause rac-Lactide ring opening copolymer by polymerized thylene carbonate alkane esterdiol to obtain, wherein said polymerized thylene carbonate alkane ester is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and poly(lactic acid) is one or both the mixing in L-type poly(lactic acid), D type poly(lactic acid).
In described styrene-maleic anhydride copolymer, the mol ratio of vinylbenzene and maleic anhydride is 2:1; The deacetylation degree of described chitin is 75%.
Compared with prior art, the invention has the beneficial effects as follows:
Signal wire degradation material provided by the invention, its formula materials have employed degradable biological material chitin, containing degradable segment poly(lactic acid), and combine the advantage of thermoplastic polyamide resin, product of the present invention is made to possess degradability, the shortcoming that the plastic material overcoming existing signal wire can not be degraded substantially, avoids environmental pollution; Overcome the shortcoming of conventional degradation material snappiness difference simultaneously, material has excellent toughness, softness, chemical-resistant, wear resistance, germ resistance, heat-resisting, the features such as product surface is smooth, make it be suitable for the manufacture of signal wire rod, the particularly manufacture of degradation material earphone wire.
Preparation method provided by the invention, rational technology, easy to operate, control accurately, be easy to industrialization.
Describe the present invention in detail below in conjunction with specific embodiment, but be not to further restriction of the present invention.
Embodiment
Embodiment 1:
Signal wire degradation material provided by the invention, it is made up of the component of following parts by weight:
Wherein, described degradable poly acid amides is prepared from by end carboxyl saturated polyester, diamine polycondensation, and wherein said end carboxyl saturated polyester is made up of polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, m-phthalic acid, stannous octoate polycondensation.
The molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000 ~ 10000g/mol, polymerized thylene carbonate alkane ester is wherein one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and poly(lactic acid) is one or both the mixing in L-type poly(lactic acid), D type poly(lactic acid); Polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol causes rac-Lactide ring opening copolymer by polymerized thylene carbonate alkane esterdiol and obtains under the effect of catalyzer, and the method is maturation method, can referenced patent ZL200910155893.6.
In described styrene-maleic anhydride copolymer, the mol ratio of vinylbenzene and maleic anhydride is 2:1, is be prepared from through solution polymerization, biodegradable.
The deacetylation degree of described chitin is 75%.
A preparation method for the degradation material of above-mentioned signal wire, it comprises the steps:
(1) degradable poly acid amides is prepared:
(11) be, polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of m-phthalic acid 1.1-1.3 takes raw material, add in reactor, 100 DEG C, vacuum hydro-extraction under 0.01Mpa, add the stannous octoate of the 0.5-1% of system material total amount afterwards, be warmed up to 200 DEG C, melt polycondensation reaction 4-6 hour, lower the temperature 100 DEG C and vacuumize 0.03Mpa, to without overhead product, obtain end carboxyl saturated polyester.
(12), end carboxyl saturated polyester 1 according to mol ratio is step (11) gained: hexamethylene-diamine 1 takes raw material, afterwards agitator is being housed, condenser, nitrogen feed pipe, pressure-regulator, drip in the reactor of tank, first add end carboxyl saturated polyester, after nitrogen purge, be heated to 180 DEG C and treat material melts, through dripping tank instillation hexamethylene-diamine, drip continuously completely under agitation 3 hours, simultaneously gradually continuous warming to reactor temperature to 250 DEG C, the moisture that period reaction produces is discharged through condenser, after hexamethylene-diamine drips, continue stirring 30 minutes at ambient pressure, heat up with speed 0.2 DEG C/min and fix hexamethylene-diamine, pass into steam afterwards and make gas phase portion pressure remain on 0.3Mpa, at temperature keeps 255 DEG C, draw off polymeric amide, cooling, packaging.
(2) raw material is taken in following ratio:
(3) all added in high speed mixer by material and mix, pour in twin screw extruder by gained mixture, controlled working temperature 170-260 DEG C, through mixing extrusion, cooling and dicing, obtains product, packaging.
Wherein, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000-10000g/mol, under the effect of catalyzer, cause rac-Lactide ring opening copolymer by polymerized thylene carbonate alkane esterdiol to obtain, wherein said polymerized thylene carbonate alkane ester is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and poly(lactic acid) is one or both the mixing in L-type poly(lactic acid), D type poly(lactic acid).
In described styrene-maleic anhydride copolymer, the mol ratio of vinylbenzene and maleic anhydride is 2:1; The deacetylation degree of described chitin is 75%.
Embodiment 2:
Degradation material of the signal wire that the present embodiment provides and preparation method thereof, it is substantially the same manner as Example 1, and its difference is:
A kind of signal wire degradation material, it is made up of the component of following parts by weight:
Wherein, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 6000g/mol, and wherein said polymerized thylene carbonate alkane ester is polyethylencarbonate, and poly(lactic acid) is L-type poly(lactic acid).
A preparation method for the degradation material of above-mentioned signal wire, its concrete mode of step (11) preparing degradable poly acid amides is as follows:
Be polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of m-phthalic acid 1.1 takes raw material, add in reactor, 100 DEG C, vacuum hydro-extraction under 0.01Mpa, add the stannous octoate of 0.5% of system material total amount afterwards, be warmed up to 200 DEG C, melt polycondensation reaction 4 hours, lower the temperature 100 DEG C and vacuumize 0.03Mpa, to without overhead product, obtain end carboxyl saturated polyester;
Step (2) takes raw material in following ratio:
Embodiment 3:
Degradation material of the signal wire that the present embodiment provides and preparation method thereof, substantially identical with embodiment 1,2, its difference is:
A degradation material for signal wire, it is made up of the component of following parts by weight:
Wherein, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000g/mol, and polymerized thylene carbonate alkane ester is wherein poly (propylene carbonate), and poly(lactic acid) is D type poly(lactic acid).
A preparation method for the degradation material of above-mentioned signal wire, its concrete mode of step (11) preparing degradable poly acid amides is as follows:
Be polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of m-phthalic acid 1.3 takes raw material, add in reactor, 100 DEG C, vacuum hydro-extraction under 0.01Mpa, add the stannous octoate of 0.8% of system material total amount afterwards, be warmed up to 200 DEG C, melt polycondensation reaction 6 hours, lower the temperature 100 DEG C and vacuumize 0.03Mpa, to without overhead product, obtain end carboxyl saturated polyester.
Step (2) takes raw material in following ratio:
Embodiment 4:
Degradation material of the signal wire that the present embodiment provides and preparation method thereof, substantially identical with embodiment 1,2,3, its difference is:
A degradation material for signal wire, it is made up of the component of following parts by weight:
Wherein, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 10000g/mol, and polymerized thylene carbonate alkane ester is wherein polymerized thylene carbonate butyl ester, and poly(lactic acid) is the 1:1 mixing in molar ratio of L-type poly(lactic acid), D type poly(lactic acid) two kinds.
A preparation method for the degradation material of above-mentioned signal wire, its concrete mode of step (11) preparing degradable poly acid amides is as follows:
Be polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of m-phthalic acid 1.2 takes raw material, add in reactor, 100 DEG C, vacuum hydro-extraction under 0.01Mpa, add the stannous octoate of 1% of system material total amount afterwards, be warmed up to 200 DEG C, melt polycondensation reaction 6 hours, lower the temperature 100 DEG C and vacuumize 0.03Mpa, to without overhead product, obtain end carboxyl saturated polyester.
Step (2) takes raw material in following ratio:
Embodiment 5:
Degradation material of the signal wire that the present embodiment provides and preparation method thereof, substantially identical with embodiment 1,2,3,4, its difference is:
A degradation material for signal wire, it is made up of the component of following parts by weight:
Wherein, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 8000g/mol, and polymerized thylene carbonate alkane ester is wherein the 1:1 mixing in molar ratio of polyethylencarbonate, poly (propylene carbonate), and poly(lactic acid) is L-type poly(lactic acid).
A preparation method for the degradation material of above-mentioned signal wire, its concrete mode of step (11) preparing degradable poly acid amides is as follows:
Be polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of m-phthalic acid 1.18 takes raw material, add in reactor, 100 DEG C, vacuum hydro-extraction under 0.01Mpa, add the stannous octoate of 0.9% of system material total amount afterwards, be warmed up to 200 DEG C, melt polycondensation reaction 5 hours, lower the temperature 100 DEG C and vacuumize 0.03Mpa, to without overhead product, obtain end carboxyl saturated polyester.
Step (2) takes raw material in following ratio:
Signal wire degradation material provided by the invention, its formula materials have employed degradable biological material chitin, containing degradable segment poly(lactic acid), and combine the advantage of thermoplastic polyamide resin, product of the present invention is made to possess degradability, the shortcoming that the plastic material overcoming existing signal wire can not be degraded substantially, there is excellent toughness, softness, chemical-resistant, wear resistance, germ resistance, heat-resisting simultaneously, the features such as product surface is smooth, it is a degradation material being suitable for very much signal wire rod, particularly earphone wire.
Preparation method provided by the invention, rational technology, easy to operate, control accurately, be easy to industrialization.
The present invention is not limited to above-mentioned embodiment, adopts the raw material identical or approximate with the above embodiment of the present invention and preparation method, and other the similar signal wire degradation materials obtained, all within protection scope of the present invention.
Claims (9)
1. a signal wire degradation material, is characterized in that, is made up of the component of following parts by weight:
2. signal wire degradation material according to claim 1, it is characterized in that, described degradable poly acid amides is prepared from by end carboxyl saturated polyester, diamine polycondensation, and wherein said end carboxyl saturated polyester is made up of polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, m-phthalic acid, stannous octoate polycondensation.
3. signal wire degradation material according to claim 2, be characterised in that, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000-10000g/mol, under the effect of catalyzer, cause rac-Lactide ring opening copolymer by polymerized thylene carbonate alkane esterdiol to obtain, wherein said polymerized thylene carbonate alkane ester is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and poly(lactic acid) is one or both the mixing in L-type poly(lactic acid), D type poly(lactic acid).
4. signal wire degradation material according to claim 1, is characterised in that, in described styrene-maleic anhydride copolymer, the mol ratio of vinylbenzene and maleic anhydride is 2:1.
5. signal wire degradation material according to claim 1, is characterised in that, the deacetylation degree of described chitin is 75%.
6. a preparation method for the signal wire degradation material that one of claim 1-5 is described, it comprises the steps:
(1) degradable poly acid amides is prepared:
(11) be, polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of m-phthalic acid 1.1-1.3 takes raw material, add in reactor, 100 DEG C, vacuum hydro-extraction under 0.01Mpa, add the stannous octoate of the 0.5-1% of system material total amount afterwards, be warmed up to 200 DEG C, melt polycondensation reaction 4-6 hour, lower the temperature 100 DEG C and vacuumize 0.03Mpa, to without overhead product, obtain end carboxyl saturated polyester.
(12), end carboxyl saturated polyester 1 according to mol ratio is step (11) gained: hexamethylene-diamine 1 takes raw material, afterwards agitator is being housed, condenser, nitrogen feed pipe, pressure-regulator, drip in the reactor of tank, first add end carboxyl saturated polyester, after nitrogen purge, be heated to 180 DEG C and treat material melts, through dripping tank instillation hexamethylene-diamine, drip continuously completely under agitation 3 hours, simultaneously gradually continuous warming to reactor temperature to 250 DEG C, the moisture that period reaction produces is discharged through condenser, after hexamethylene-diamine drips, continue stirring 30 minutes at ambient pressure, heat up with speed 0.2 DEG C/min and fix hexamethylene-diamine, pass into steam afterwards and make gas phase portion pressure remain on 0.3Mpa, at temperature keeps 255 DEG C, draw off polymeric amide, cooling, packaging,
(2) raw material is taken in following ratio:
(3) all added in high speed mixer by material and mix, pour in twin screw extruder by gained mixture, controlled working temperature 170-260 DEG C, through mixing extrusion, cooling and dicing, obtains product, packaging.
7. the preparation method of signal wire degradation material according to claim 6, it is characterized in that, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000-10000g/mol, under the effect of catalyzer, cause rac-Lactide ring opening copolymer by polymerized thylene carbonate alkane esterdiol to obtain, wherein said polymerized thylene carbonate alkane ester is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and poly(lactic acid) is one or both the mixing in L-type poly(lactic acid), D type poly(lactic acid).
8. the preparation method of signal wire degradation material according to claim 6, is characterized in that, in described styrene-maleic anhydride copolymer, the mol ratio of vinylbenzene and maleic anhydride is 2:1.
9. the preparation method of signal wire degradation material according to claim 6, is characterized in that, the deacetylation degree of described chitin is 75%.
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| CN201410452039.7A CN104212166B (en) | 2014-09-05 | 2014-09-05 | A kind of holding wire degradation material and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181098A (en) * | 1995-04-07 | 1998-05-06 | 生物技术生物学自然包装有限公司 | Biologically degradable polymer mixture |
| CN101735433A (en) * | 2009-12-29 | 2010-06-16 | 徐玉华 | Poly(alkene carbonate) diol-poly(lactic acid) block copolymer and preparation method thereof |
| CN103804860A (en) * | 2012-11-07 | 2014-05-21 | 李雪娇 | Novel plastic |
-
2014
- 2014-09-05 CN CN201410452039.7A patent/CN104212166B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181098A (en) * | 1995-04-07 | 1998-05-06 | 生物技术生物学自然包装有限公司 | Biologically degradable polymer mixture |
| CN101735433A (en) * | 2009-12-29 | 2010-06-16 | 徐玉华 | Poly(alkene carbonate) diol-poly(lactic acid) block copolymer and preparation method thereof |
| CN103804860A (en) * | 2012-11-07 | 2014-05-21 | 李雪娇 | Novel plastic |
Non-Patent Citations (1)
| Title |
|---|
| 朱颖先等: "可生物降解型纤维材料", 《高分子通报》 * |
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