CN104212166B - A kind of holding wire degradation material and preparation method thereof - Google Patents
A kind of holding wire degradation material and preparation method thereof Download PDFInfo
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- CN104212166B CN104212166B CN201410452039.7A CN201410452039A CN104212166B CN 104212166 B CN104212166 B CN 104212166B CN 201410452039 A CN201410452039 A CN 201410452039A CN 104212166 B CN104212166 B CN 104212166B
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- 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 kind of holding wire degradation material, it is made up of the component of following parts by weight: degradable poly amide: 50-60 part；PTMG: 30-40 part；Chitin: 8-10 part；Styrene-maleic anhydride copolymer: 10-20 part；Fluorosioloxane rubber: 3-5 part；Nanometer calcium sulfate: 10-20 part；Described degradable poly amide is formed by end carboxyl saturated polyester, diamine polycondensation, and described end carboxyl saturated polyester is formed by polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, M-phthalic acid, stannous octoate polycondensation；Also disclose its preparation method, prepare containing raw material, weigh, mix extrusion, pelletize packaging and other steps.The present invention contains degradable molecule segment and combines the advantage of thermoplastic polyamide resin, make product possess degradability, excellent toughness, softness, chemical-resistant, wearability, antibiotic property, heat-resisting, the features such as product surface is smooth, are suitable for the manufacture of signal wire rod such as earphone wire.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of holding 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 construction featuress, and this type of product yield is big, volume is little, recovery is difficult, after discarded, easily cause environmental pollution.
Polyamide thermoplastic elastomeric material is because of features such as its machinability, rubber and plastic characteristic, toughness, and the designability of its molecular structure is strong simultaneously, selects different molecule segments to design its hard section, the structure of soft section so that it is to meet the application of different occasions.
But, existing most of thermoplastic plastic's materials, all can not degrade；And existing a lot of degradation plastic, its pliability is all poor, is not suitable for again manufacturing signal wire rod.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide the holding wire degradation material of the advantages such as a kind of biodegradable, excellent toughness, softness, chemical-resistant, antibiotic property, product surface be smooth.
The present invention also aims to provide the industrialized process for preparing of above-mentioned holding wire degradation material.
The above-mentioned purpose of the present invention is achieved by the following technical solution:
A kind of holding wire degradation material, it is made up of the component of following parts by weight:
Wherein, described degradable poly amide is to be 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 therein is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and polylactic acid is one or both the mixing in L-type polylactic acid, D type polylactic acid；Polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is caused lactide ring opening copolymer to obtain by polymerized thylene carbonate alkane esterdiol under the effect of catalyst, and the method is maturation method, is referred to patent ZL200910155893.6.
In described styrene-maleic anhydride copolymer, styrene is 2:1 with the mol ratio of maleic anhydride, is be prepared from through polymerisation in solution, biodegradable.
The deacetylation degree of described chitin is 75%.
The preparation method of a kind of described holding wire degradation material, it comprises the steps:
(1) degradable poly amide is prepared:
(11) it is, 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 weighs raw material, add in reactor, 100 DEG C, vacuum dehydration under 0.01Mpa, add the stannous octoate of the 0.5-1% of system material total amount afterwards, it is warmed up to 200 DEG C, melt polycondensation reaction 4-6 hour, lower the temperature 100 DEG C of evacuation 0.03Mpa, to without distillation, obtaining end carboxyl saturated polyester.
(12), end carboxyl saturated polyester 1 according to mol ratio is step (11) gained: hexamethylene diamine 1 weighs raw material, afterwards equipped with agitator, condenser, nitrogen feed pipe, pressure regulator, in the reactor of dropping tank, it is initially charged end carboxyl saturated polyester, after nitrogen purge, it is heated to 180 DEG C and treats material melts, hexamethylene diamine is instilled through dropping tank, in under agitation 3 hours, dropping is complete continuously, simultaneously gradually continuous warming to reactor temperature to 250 DEG C, the condensed device of moisture that period reaction produces is discharged, after hexamethylene diamine drips, continue stirring 30 minutes at ambient pressure, heat up with 0.2 DEG C/min of speed and fix hexamethylene diamine, pass into steam afterwards and make gas phase portion pressure be maintained at 0.3Mpa, at temperature keeps 255 DEG C, draw off polyamide, cooling, packaging.
(2) raw material is weighed in following ratio:
(3) material is all added mix homogeneously in high speed mixer, gained mixture is poured in double screw extruder, control processing temperature 170-260 DEG C, through mixing extrusion, cooling and dicing, obtain product, packaging.
Wherein, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000-10000g/mol, it is caused lactide ring opening copolymer to obtain under the effect of catalyst by polymerized thylene carbonate alkane esterdiol, wherein said polymerized thylene carbonate alkane ester is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and polylactic acid is one or both the mixing in L-type polylactic acid, D type polylactic acid.
In described styrene-maleic anhydride copolymer, styrene is 2:1 with the mol ratio of maleic anhydride；The deacetylation degree of described chitin is 75%.
Compared with prior art, the invention has the beneficial effects as follows:
Holding wire degradation material provided by the invention, its formula materials have employed degradable biological material chitin, containing degradable segment polylactic acid, and combine the advantage of thermoplastic polyamide resin, product of the present invention is made to possess degradability, overcome the shortcoming that the plastic material of existing holding wire can not be degraded substantially, it is to avoid environmental pollution；The shortcoming simultaneously overcoming conventional degradation material pliability difference, material has the toughness of excellence, softness, chemical-resistant, wearability, antibiotic property, heat-resisting, the features such as product surface is smooth so that it is be suitable for signal wire rod manufacture, the particularly manufacture of degradation material earphone wire.
Preparation method provided by the invention, rational technology, easy to operate, control accurately, it is easy to industrialization.
The present invention is described in detail below in conjunction with specific embodiment, but is not the further restriction to the present invention.
Detailed description of the invention
Embodiment 1:
Holding wire degradation material provided by the invention, it is made up of the component of following parts by weight:
Wherein, described degradable poly amide is to be 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 therein is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and polylactic acid is one or both the mixing in L-type polylactic acid, D type polylactic acid；Polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is caused lactide ring opening copolymer to obtain by polymerized thylene carbonate alkane esterdiol under the effect of catalyst, and the method is maturation method, is referred to patent ZL200910155893.6.
In described styrene-maleic anhydride copolymer, styrene is 2:1 with the mol ratio of maleic anhydride, is be prepared from through polymerisation in solution, biodegradable.
The deacetylation degree of described chitin is 75%.
The preparation method of the degradation material of a kind of above-mentioned holding wire, it comprises the steps:
(1) degradable poly amide is prepared:
(11) it is, 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 weighs raw material, add in reactor, 100 DEG C, vacuum dehydration under 0.01Mpa, add the stannous octoate of the 0.5-1% of system material total amount afterwards, it is warmed up to 200 DEG C, melt polycondensation reaction 4-6 hour, lower the temperature 100 DEG C of evacuation 0.03Mpa, to without distillation, obtaining end carboxyl saturated polyester.
(12), end carboxyl saturated polyester 1 according to mol ratio is step (11) gained: hexamethylene diamine 1 weighs raw material, afterwards equipped with agitator, condenser, nitrogen feed pipe, pressure regulator, in the reactor of dropping tank, it is initially charged end carboxyl saturated polyester, after nitrogen purge, it is heated to 180 DEG C and treats material melts, hexamethylene diamine is instilled through dropping tank, in under agitation 3 hours, dropping is complete continuously, simultaneously gradually continuous warming to reactor temperature to 250 DEG C, the condensed device of moisture that period reaction produces is discharged, after hexamethylene diamine drips, continue stirring 30 minutes at ambient pressure, heat up with 0.2 DEG C/min of speed and fix hexamethylene diamine, pass into steam afterwards and make gas phase portion pressure be maintained at 0.3Mpa, at temperature keeps 255 DEG C, draw off polyamide, cooling, packaging.
(2) raw material is weighed in following ratio:
(3) material is all added mix homogeneously in high speed mixer, gained mixture is poured in double screw extruder, control processing temperature 170-260 DEG C, through mixing extrusion, cooling and dicing, obtain product, packaging.
Wherein, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000-10000g/mol, it is caused lactide ring opening copolymer to obtain under the effect of catalyst by polymerized thylene carbonate alkane esterdiol, wherein said polymerized thylene carbonate alkane ester is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and polylactic acid is one or both the mixing in L-type polylactic acid, D type polylactic acid.
In described styrene-maleic anhydride copolymer, styrene is 2:1 with the mol ratio of maleic anhydride；The deacetylation degree of described chitin is 75%.
Embodiment 2:
Degradation material of holding wire that the present embodiment provides and preparation method thereof, it is substantially the same manner as Example 1, and it is different in that:
A kind of holding 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 polylactic acid is L-type polylactic acid.
A kind of preparation method of the degradation material of above-mentioned holding wire, its concrete mode of step (11) preparing degradable poly amide is as follows:
It is polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of M-phthalic acid 1.1 weighs raw material, add in reactor, 100 DEG C, vacuum dehydration under 0.01Mpa, the stannous octoate of the 0.5% of addition system material total amount afterwards, it is warmed up to 200 DEG C, melt polycondensation reaction 4 hours, lower the temperature 100 DEG C of evacuation 0.03Mpa, to without distillation, obtaining end carboxyl saturated polyester；
Step (2) weighs raw material in following ratio:
Embodiment 3:
Degradation material of holding wire that the present embodiment provides and preparation method thereof, essentially identical with embodiment 1,2, it is different in that:
A kind of degradation material of holding 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 therein is poly (propylene carbonate), and polylactic acid is D type polylactic acid.
A kind of preparation method of the degradation material of above-mentioned holding wire, its concrete mode of step (11) preparing degradable poly amide is as follows:
It is polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of M-phthalic acid 1.3 weighs raw material, add in reactor, 100 DEG C, vacuum dehydration under 0.01Mpa, the stannous octoate of the 0.8% of addition system material total amount afterwards, it is warmed up to 200 DEG C, melt polycondensation reaction 6 hours, lower the temperature 100 DEG C of evacuation 0.03Mpa, to without distillation, obtaining end carboxyl saturated polyester.
Step (2) weighs raw material in following ratio:
Embodiment 4:
Degradation material of holding wire that the present embodiment provides and preparation method thereof, essentially identical with embodiment 1,2,3, it is different in that:
A kind of degradation material of holding 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 therein is polymerized thylene carbonate butyl ester, and polylactic acid is L-type polylactic acid, D type polylactic acid two kinds 1:1 in molar ratio mixing.
A kind of preparation method of the degradation material of above-mentioned holding wire, its concrete mode of step (11) preparing degradable poly amide is as follows:
It is polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of M-phthalic acid 1.2 weighs raw material, add in reactor, 100 DEG C, vacuum dehydration under 0.01Mpa, the stannous octoate of the 1% of addition system material total amount afterwards, it is warmed up to 200 DEG C, melt polycondensation reaction 6 hours, lower the temperature 100 DEG C of evacuation 0.03Mpa, to without distillation, obtaining end carboxyl saturated polyester.
Step (2) weighs raw material in following ratio:
Embodiment 5:
Degradation material of holding wire that the present embodiment provides and preparation method thereof, essentially identical with embodiment 1,2,3,4, it is different in that:
A kind of degradation material of holding 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 therein is polyethylencarbonate, poly (propylene carbonate) 1:1 in molar ratio mixing, and polylactic acid is L-type polylactic acid.
A kind of preparation method of the degradation material of above-mentioned holding wire, its concrete mode of step (11) preparing degradable poly amide is as follows:
It is polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol 1 according to mol ratio: the ratio of M-phthalic acid 1.18 weighs raw material, add in reactor, 100 DEG C, vacuum dehydration under 0.01Mpa, the stannous octoate of the 0.9% of addition system material total amount afterwards, it is warmed up to 200 DEG C, melt polycondensation reaction 5 hours, lower the temperature 100 DEG C of evacuation 0.03Mpa, to without distillation, obtaining end carboxyl saturated polyester.
Step (2) weighs raw material in following ratio:
Holding wire degradation material provided by the invention, its formula materials have employed degradable biological material chitin, containing degradable segment polylactic acid, and combine the advantage of thermoplastic polyamide resin, product of the present invention is made to possess degradability, overcome the shortcoming that the plastic material of existing holding wire can not be degraded substantially, there is the toughness of excellence simultaneously, softness, chemical-resistant, wearability, antibiotic property, heat-resisting, the features such as product surface is smooth, it it is a degradation material being highly suitable for signal wire rod, particularly earphone wire.
Preparation method provided by the invention, rational technology, easy to operate, control accurately, it is 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 holding wire degradation materials obtained, all within protection scope of the present invention.
Claims (8)
1. a holding wire degradation material, it is characterised in that be made up of the component of following parts by weight:
Described degradable poly amide is to be 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.
2. holding wire degradation material according to claim 1, it is characterised by, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000-10000g/mol, it is caused lactide ring opening copolymer to obtain under the effect of catalyst by polymerized thylene carbonate alkane esterdiol, wherein said polymerized thylene carbonate alkane ester is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and polylactic acid is one or both the mixing in L-type polylactic acid, D type polylactic acid.
3. holding wire degradation material according to claim 1, is characterised by, in described styrene-maleic anhydride copolymer, styrene is 2:1 with the mol ratio of maleic anhydride.
4. holding wire degradation material according to claim 1, is characterised by, the deacetylation degree of described chitin is 75%.
5. a preparation method for holding wire degradation material described for one of claim 1-4, it comprises the steps:
(1) degradable poly amide is prepared:
(11), according to polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol: the ratio that M-phthalic acid mol ratio is 1:1.1-1.3 weighs raw material, add in reactor, 100 DEG C, vacuum dehydration under 0.01Mpa, add the stannous octoate of the 0.5-1% of system material integral molar quantity afterwards, it is warmed up to 200 DEG C, melt polycondensation reaction 4-6 hour, lower the temperature 100 DEG C of evacuation 0.03Mpa, to without distillation, obtaining end carboxyl saturated polyester；
(12), end carboxyl saturated polyester according to step (11) gained: hexamethylene diamine mol ratio is that 1:1 weighs raw material, afterwards equipped with agitator, condenser, nitrogen feed pipe, pressure regulator, in the reactor of dropping tank, it is initially charged end carboxyl saturated polyester, after nitrogen purge, it is heated to 180 DEG C and treats material melts, hexamethylene diamine is instilled through dropping tank, in under agitation 3 hours, dropping is complete continuously, simultaneously gradually continuous warming to reactor temperature to 250 DEG C, the condensed device of moisture that period reaction produces is discharged, after hexamethylene diamine drips, continue stirring 30 minutes at ambient pressure, heat up with 0.2 DEG C/min of speed and fix hexamethylene diamine, pass into steam afterwards and make gas phase portion pressure be maintained at 0.3Mpa, at temperature keeps 255 DEG C, draw off polyamide, cooling, packaging；
(2) raw material is weighed in following ratio:
(3) material is all added mix homogeneously in high speed mixer, gained mixture is poured in double screw extruder, control processing temperature 170-260 DEG C, through mixing extrusion, cooling and dicing, obtain product, packaging.
6. the preparation method of holding wire degradation material according to claim 5, it is characterized in that, the molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000-10000g/mol, it is caused lactide ring opening copolymer to obtain under the effect of catalyst by polymerized thylene carbonate alkane esterdiol, wherein said polymerized thylene carbonate alkane ester is one or more in polyethylencarbonate, poly (propylene carbonate), polymerized thylene carbonate butyl ester, and polylactic acid is one or both the mixing in L-type polylactic acid, D type polylactic acid.
7. the preparation method of holding wire degradation material according to claim 5, it is characterised in that in described styrene-maleic anhydride copolymer, styrene is 2:1 with the mol ratio of maleic anhydride.
8. the preparation method of holding wire degradation material according to claim 5, it is characterised in that the deacetylation degree of described chitin is 75%.
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