CN103484969A - Tail end-capped polylactic acid fiber with high heat resistance and water resistance and preparation method thereof - Google Patents
Tail end-capped polylactic acid fiber with high heat resistance and water resistance and preparation method thereof Download PDFInfo
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- CN103484969A CN103484969A CN201310356473.0A CN201310356473A CN103484969A CN 103484969 A CN103484969 A CN 103484969A CN 201310356473 A CN201310356473 A CN 201310356473A CN 103484969 A CN103484969 A CN 103484969A
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Abstract
The invention discloses a polylactic acid fiber which has high hydrolysis resistance and friction resistance. The polylactic acid fiber comprises a polylactic acid ingredient, wherein the group at the tail end of a polylactic acid molecular chain is capped, glycidyl ester is used as an epoxy capping agent, and the polylactic acid ingredient is mixed with fatty acid diamide and/or an alkyl substituted type fatty acid monoamide ingredient and a polycarbodiimide ingredient.
Description
Technical field:
The present invention relates to a kind of novel high hydrolysis resistance and high friction resistance polylactic acid fibre and preparation method.
Background technology:
In recent years, along with the raising of people's living standard and the enhancing of environmental consciousness, people more and more pay attention to the research of natural Biodegradable fibers, new environmental protection fiber is is competitively researched and developed in countries in the world, wherein in late nineteen nineties, just realized that the acid fiber by polylactic (PLA fiber) of industrialized developing is the most noticeable, PLA (PLA) is that a class can be degradable, environment amenable aliphatic polyester series macromolecular material, there is good biocompatibility, through enzyme, decompose in vivo, in vitro can be in microorganism, water, acid, under the effect such as alkali, decompose fully, end product is carbon dioxide and water, and burning the time can not be distributed poison gas, can not pollute.
But, just because of the natural sex of acid fiber by polylactic, inevitably have some shortcomings.Acid fiber by polylactic has superior degradability, cause its resistant to hydrolysis performance poor, in the dyeing course of fabric, through pressurized high-temperature, process, the intensity of its fabric can descend, and acid fiber by polylactic has the shortcoming that skin-friction coefficient is high, wear no resistance simultaneously, the crock fastness of for example stipulating according to JIS L0849, the garment material General Requirements is more than 3 grades, but present acid fiber by polylactic only has 1 grade low-level, has affected the extensive use of acid fiber by polylactic.
The example that simultaneously adds hydrolysis-resisting agent and lubricant in the PLA fiber is few, for example toray Co., Ltd. reports in the patent (application number is 03820140.2) of China's application, this technology is to add aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide with respect to fabric integer 0.1-5% weight in acid fiber by polylactic, can improve the rub resistance of PLA after adding, but can not improve the anti-water-based that adds of PLA.Report in No. 11-80522, the Japanese kokai publication hei of for example Japanese Misshin Spinning Co., Ltd application again, this technology is to have added the polycarbodiimide group in acid fiber by polylactic, add the rear anti-water-based energy that adds that has improved PLA, but rub resistance is not improved.The hydrolysis-resisting agent that the present invention adds simultaneously and lubricant composition, both can improve the anti-water-based energy that adds of PLA, can improve again the crocking resistance of PLA.
Summary of the invention:
The object of the present invention is to provide a kind of resistant to hydrolysis performance, high hydrolysis resistance, high friction resistance polylactic acid fibre and preparation method that crocking resistance is good.
Technical solution of the present invention is:
A kind of high hydrolysis resistance, high friction resistance polylactic acid fibre, comprise the PLA composition, it is characterized in that: in the PLA composition, the end group of polylactic acid molecule chain is closing form, take the ethylene oxidic ester class as epoxy-capped dose, in the PLA composition, be mixed with aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition and polycarbodiimide composition.
Contain-N=C=N-of polycarbodiimide group, shown in the following structural formula of feature structure formula
The straight chain that R1, R2 are the saturated of C1～C10 or unsaturated alkyl group, C3～C20 or with the alkyl group of side chain or ring-type and one or more in the C6-C20 aromatic group
The polycarbodiimide mean molecule quantity is 3000～50000.
The polycarbodiimide composition is 0.5～10% of PLA weight.
In high hydrolysis resistance and high friction resistance polylactic acid fibre, the fusing point of aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition is more than 80 ℃.
In high hydrolysis resistance and high friction resistance polylactic acid fibre, aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition are 0.1～10% of PLA weight.
Terminal carboxyl group content is 1～20eq/ton, and mean molecule quantity is 50000～300000, and after the High Temperature High Pressure hot water treatment, its strength retention is 60～95%.
High hydrolysis resistance and high friction resistance polylactic acid fibre surface have the lubricant that at least one is selected from fatty acid ester, polyol ester, ether-ether, siloxanes, mineral oil.
The preparation method of a kind of high hydrolysis resistance, high friction resistance polylactic acid fibre is characterized in that: comprise the following steps:
(1) by polylactic acid slice through vacuumize, to moisture be 30～500ppm;
(2) dried polylactic acid slice and polycarbodiimide composition and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition are mixed, with the double screw extruder melt blending, extrude, make the master batch section;
(3) by master batch chip drying to moisture, be 50～400ppm;
(4) will and be mixed through the dried polylactic acid slice of step (1) through the dried master batch section of step (3), 0.5～10% and the aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide composition that make the polycarbodiimide composition account for PLA weight account for 0.1～10% of PLA weight, by single composition spinning machine melt spinning, obtain the preliminary draft silk;
(5) the preliminary draft silk is extended, must be extended silk.
In step (2), extrusion temperature is: 170～240 ℃, screw speed is 200～400rpm; In step (4), spinning temperature is 200～250 ℃, and winding speed is 2500～5000m/min; In step (5), extension ratio is 1.3～2.0.
The preparation method of a kind of high hydrolysis resistance, high friction resistance polylactic acid fibre is characterized in that: comprise the following steps:
(1) by polylactic acid slice through vacuumize, to moisture be 30～500ppm;
(2) dried polylactic acid slice and 0.5～10% the polycarbodiimide composition that is equivalent to PLA weight and 0.1～10% aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide composition that are equivalent to PLA weight are mixed, with the double screw extruder melt blending, extrude, granulation;
(3) by chip drying to the moisture obtained, be 50～400ppm;
(4) will carry out melt spinning through the dried section of step (3), obtain the preliminary draft silk;
(5) the preliminary draft silk is extended, must be extended silk.
In step (2), extrusion temperature is: 170～240 ℃, screw speed is 200～400rpm; In step (4), spinning temperature is 200～250 ℃, and winding speed is 2500～5000m/min; In step (5), extension ratio is 1.3～2.0.
High hydrolysis resistance of the present invention and high friction resistance polylactic acid fibre, added Effective Anti hydrolytic reagent polycarbodiimide composition and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition in the PLA composition, resistant to hydrolysis group composition is-N=C=N-.The hydrolysis-resisting agent polycarbodiimide accounts for 0.5%～10% of PLA weight, can make the carboxyl-content of acid fiber by polylactic reach 1～20eq/ton, and through the hot water treatment of 120 ℃ 30 minutes, its strength retention was 60～95%.Aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition account for 0.1%～10% of PLA weight, rub resistance that can acid fiber by polylactic is improved, in the evaluation of fabric, after dyeing, by the evaluation of friction colorfastness, the friction fastness of fabric reaches the 4-5 level.The friction fastness evaluation method of above-mentioned fabric, adopt A-I method in JIS L0849 (friction colorfastness test method).
High hydrolysis resistance of the present invention and high friction resistance polylactic acid fibre are owing to having very high hydrolytic resistance and good wear-resisting wiping, can improve the rub resistance of acid fiber by polylactic in fabric processing and at high temperature, add the performance of depressing dyeing, and PLA own just has biodegradability, can improve the extensive use of acid fiber by polylactic.
Below in conjunction with embodiment, the invention will be further described:
The specific embodiment:
Embodiment 1:
By polylactic acid slice through vacuumize, to moisture be 100ppm, by dried polylactic acid slice be equivalent to the 10% polycarbodiimide compound Stabaxol P200 (TUV company product) of PLA weight and be equivalent to the 7.5%EBS (ethylene bis stearamide of PLA weight, its fusing point is 144 ℃) mix, with double screw extruder melt blending, extruding pelletization, extrusion temperature is 200 ℃, and screw speed is 250rpm, makes the master batch section.Then to master batch, drying is carried out in section, make master batch section moisture reach 120ppm, again through melt spinning, prepared by the section of the master batch of dried polylactic acid slice 60% weight and 40% weight, the spinning oil emulsion that is 15% by concentration by the thread guide that oils is applied on fiber, the spinning oil emulsion is to be mixed by the spinning oil and the water that contain 40% wt fat acid esters base lubricant (octyl palmitate of the stearic acid isotridecyl ester of 20% weight+20% weight), and the final oil content that makes fiber is 1%.Spinning temperature is 210 ℃, and winding speed is 2800m/min, is finally extended, and extension ratio is 1.5, obtains product.The carboxyl-content of its fiber is 7eq/ton, through 30 minutes strength retentions of 120 ℃ of hot water treatment, is 75%.Make fabric dyed after, the friction fastness reach 4 grades.
Embodiment 2:
By polylactic acid slice through vacuumize, to moisture be 80ppm, by dried polylactic acid slice be equivalent to the 12% polycarbodiimide compound Stabaxol P200 (TUV company product) of PLA weight and be equivalent to the 10%EBS (ethylene bis stearamide of PLA weight, its fusing point is 144 ℃) mix, with double screw extruder melt blending, extruding pelletization, extrusion temperature is 190 ℃, and screw speed is 300rpm, makes the master batch section.Then to master batch, drying is carried out in section, make master batch section moisture reach 100ppm, again through melt spinning, prepared by the section of the master batch of dried polylactic acid slice 65% weight and 35% weight, the spinning oil emulsion that is 15% by concentration by the thread guide that oils is applied on fiber, the spinning oil emulsion is to be mixed by the spinning oil and the water that contain 40% wt fat acid esters base lubricant (octyl palmitate of the stearic acid isotridecyl ester of 20% weight+20% weight), and the final oil content that makes fiber is 0.7%.Spinning temperature is 215 ℃, and winding speed is 3600m/min, is finally extended, and extension ratio is 1.3, obtains product.The carboxyl-content of its fiber is 4eq/ton, through 30 minutes strength retentions of 120 ℃ of hot water treatment, is 80%.Make fabric dyed after, the friction fastness reach 5 grades.
Embodiment 3:
By polylactic acid slice through vacuumize, to moisture be 120ppm, by dried polylactic acid slice be equivalent to the 2% polycarbodiimide compound Stabaxol P200 (TUV company product) of PLA weight and be equivalent to the 0.5%EBS (ethylene bis stearamide of PLA weight, its fusing point is 144 ℃) composition mixes, with the double screw extruder melt blending, extrude, granulation, extrusion temperature is 200 ℃, and screw speed is 250rpm.Then the section obtained is carried out to drying, the moisture that makes to cut into slices reaches 150ppm, through melt spinning, prepare, the spinning oil emulsion that is 15% by concentration by the thread guide that oils is applied on fiber, the spinning oil emulsion is to be mixed by the spinning oil and the water that contain 40% wt fat acid esters base lubricant (octyl palmitate of the stearic acid isotridecyl ester of 20% weight+20% weight), and the final oil content that makes fiber is 0.8%.Spinning temperature is 220 ℃, and winding speed is 3000m/min, is finally extended, and extension ratio is 1.4, obtains product.The carboxyl-content of its fiber is 5eq/ton, through 30 minutes strength retentions of 120 ℃ of hot water treatment, is 80%.Make fabric dyed after, the friction fastness reach 4 grades.
Embodiment 4:
By polylactic acid slice through vacuumize, to moisture be 100ppm, by dried polylactic acid slice be equivalent to the 1% polycarbodiimide compound Stabaxol P200 (TUV company product) of PLA weight and be equivalent to the 0.7%EBS (ethylene bis stearamide of PLA weight, its fusing point is 144 ℃) composition mixes, with the double screw extruder melt blending, extrude, granulation, extrusion temperature is 210 ℃, and screw speed is 280rpm.Then the section obtained is carried out to drying, the moisture that makes to cut into slices reaches 120ppm, through melt spinning, prepare, the spinning oil emulsion that is 15% by concentration by the thread guide that oils is applied on fiber, the spinning oil emulsion is to be mixed by the spinning oil and the water that contain 40% wt fat acid esters base lubricant (octyl palmitate of the stearic acid isotridecyl ester of 20% weight+20% weight), and the final oil content that makes fiber is 0.5%.Spinning temperature is 225 ℃, and winding speed is 2800m/min, is finally extended, and extension ratio is 1.5, obtains product.The carboxyl-content of its fiber is 8eq/ton, through 30 minutes strength retentions of 120 ℃ of hot water treatment, is 70%.Make fabric dyed after, the friction fastness reach 5 grades.
The present invention can have other embodiment, contain-N=C=N-of its polycarbodiimide group, shown in the following structural formula of feature structure formula:
Its R1, R2 are specifically as follows:
The straight chain that R1, R2 are the saturated of C1～C10 or unsaturated alkyl group, C3～C20 or, with the alkyl group of side chain or ring-type and one or more in the C6-C20 aromatic group, example: R1 is methylene group, R2 is that 2,6-dimethyl is to phenylene group; Or R1 is the Ya Xinji group, R2 is 3-methyl metaphenylene group; Or R1 is the allylidene group, R2 is that 2-vinyl-6-methyl is to phenylene group; Or R1 is cyclohexyl groups, R2 is the methylene phenyl group; Or R1 is 2,3-dimethyl-butylidene group, R2 is 2,6-dimethylated methylene phenyl group; Or R1 be 2,6-dimethyl to phenylene group, R2 is methylene group; Or R1 is 3-methyl metaphenylene group, R2 is the Ya Xinji group; Or R1 be 2-vinyl-6-methyl to phenylene group, R2 is the allylidene group; Or R1 is the methylene phenyl group, R2 is cyclohexyl groups; Or R1 is 2,6-dimethylated methylene phenyl group, R2 is 2,3-dimethyl-butylidene group; Or R1 be 2,6-dimethyl to phenylene group, R2 is 2,3-dimethyl-butylidene group; Or R1 is the Ya Xinji group, R2 is cyclohexyl groups.
Claims (10)
1. a high hydrolysis resistance, high friction resistance polylactic acid fibre, comprise the PLA composition, it is characterized in that: the end group of polylactic acid molecule chain is closing form, take the ethylene oxidic ester class as epoxy-capped dose, in the PLA composition, be mixed with aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition and polycarbodiimide composition.
2. high hydrolysis resistance according to claim 1, high friction resistance polylactic acid fibre is characterized in that: contain-N=C=N-of polycarbodiimide group, and shown in the following structural formula of feature structure formula
The straight chain that R1, R2 are the saturated of C1～C10 or unsaturated alkyl group, C3～C20 or with the alkyl group of side chain or ring-type and one or more in the C6-C20 aromatic group; The polycarbodiimide mean molecule quantity is 3000～50000.
3. high hydrolysis resistance according to claim 1 and 2, high friction resistance polylactic acid fibre, it is characterized in that: the polycarbodiimide composition is 0.5～10% of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition are 0.1～10% of PLA weight.
4. high hydrolysis resistance according to claim 1 and 2, high friction resistance polylactic acid fibre, it is characterized in that: wherein the fusing point of aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition is more than 80 ℃.
5. high hydrolysis resistance according to claim 1 and 2 and high friction resistance polylactic acid fibre, it is characterized in that: terminal carboxyl group content is 1～20eq/ton, mean molecule quantity is 50000～300000, and after the High Temperature High Pressure hot water treatment, its strength retention is 60～95%.
6. high hydrolysis resistance according to claim 1 and 2, high friction resistance fiber, is characterized in that: at fiber surface, have the lubricant that at least one is selected from fatty acid ester, polyol ester, ether-ether, siloxanes, mineral oil.
7. the preparation method of a high hydrolysis resistance, high friction resistance polylactic acid fibre, is characterized in that: comprise the following steps:
(1) by polylactic acid slice through vacuumize, to moisture be 30～500ppm;
(2) dried polylactic acid slice and polycarbodiimide composition and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition are mixed, with the double screw extruder melt blending, extrude, make the master batch section;
(3) by master batch chip drying to moisture, be 50～400ppm;
(4) will and be mixed through the dried polylactic acid slice of step (1) through the dried master batch section of step (3), 0.5～10% and the aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide composition that make the polycarbodiimide composition account for PLA weight account for 0.1～10% of PLA weight, by single composition spinning machine melt spinning, obtain the preliminary draft silk;
(5) the preliminary draft silk is extended, must be extended silk.
8. the preparation method of high hydrolysis resistance according to claim 7, high friction resistance polylactic acid fibre is characterized in that: in step (2), extrusion temperature is: 170～240 ℃, screw speed is 200～400rpm; In step (4), spinning temperature is 200～250 ℃, and winding speed is 2500～5000m/min; In step (5), extension ratio is 1.3～2.0.
9. the preparation method of a high hydrolysis resistance, high friction resistance polylactic acid fibre, is characterized in that: comprise the following steps:
(1) by polylactic acid slice through vacuumize, to moisture be 30～500ppm;
(2) dried polylactic acid slice and 0.5～10% the polycarbodiimide composition that is equivalent to PLA weight and 0.1～10% aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide composition that are equivalent to PLA weight are mixed, with the double screw extruder melt blending, extrude, granulation;
(3) by chip drying to the moisture obtained, be 50～400ppm;
(4) will carry out melt spinning through the dried section of step (3), obtain the preliminary draft silk;
(5) the preliminary draft silk is extended, must be extended silk.
10. the preparation method of high hydrolysis resistance according to claim 9, high friction resistance polylactic acid fibre is characterized in that: in step (2), extrusion temperature is: 170～240 ℃, screw speed is 200～400rpm; In step (4), spinning temperature is 200～250 ℃, and winding speed is 2500～5000m/min; In step (5), extension ratio is 1.3～2.0.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112877809A (en) * | 2021-03-12 | 2021-06-01 | 苏州龙杰特种纤维股份有限公司 | Novel polylactic acid fiber and preparation method thereof |
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| CN101368297A (en) * | 2007-08-15 | 2009-02-18 | 东丽纤维研究所（中国）有限公司 | High hydrolysis resistance, high friction resistance polylactic acid fibre and preparation method |
| CN101851808A (en) * | 2009-04-02 | 2010-10-06 | 东丽纤维研究所（中国）有限公司 | Hydrolytic-resistant modified polylactic acid fiber and preparation method thereof |
| CN102286801A (en) * | 2011-05-27 | 2011-12-21 | 东华大学 | Preparation method of flexible PLA (Polylactic Acid) fibers with efficient hydrolytic resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368297A (en) * | 2007-08-15 | 2009-02-18 | 东丽纤维研究所（中国）有限公司 | High hydrolysis resistance, high friction resistance polylactic acid fibre and preparation method |
| CN101851808A (en) * | 2009-04-02 | 2010-10-06 | 东丽纤维研究所（中国）有限公司 | Hydrolytic-resistant modified polylactic acid fiber and preparation method thereof |
| CN102286801A (en) * | 2011-05-27 | 2011-12-21 | 东华大学 | Preparation method of flexible PLA (Polylactic Acid) fibers with efficient hydrolytic resistance |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112877809A (en) * | 2021-03-12 | 2021-06-01 | 苏州龙杰特种纤维股份有限公司 | Novel polylactic acid fiber and preparation method thereof |
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Application publication date: 20140101 |