CN104695047B - A kind of high flexibility acid fiber by polylactic composite material and preparation method - Google Patents
A kind of high flexibility acid fiber by polylactic composite material and preparation method Download PDFInfo
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- CN104695047B CN104695047B CN201310666327.8A CN201310666327A CN104695047B CN 104695047 B CN104695047 B CN 104695047B CN 201310666327 A CN201310666327 A CN 201310666327A CN 104695047 B CN104695047 B CN 104695047B
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Abstract
The present invention relates to a kind of high flexibility acid fiber by polylactic composite material and preparation method, which is contained the following parts by weight: 70 parts -90 parts of polylactic acid (PLA), 1 part -30 parts of polypropylene glycol adipate (PPA), 0.1 part -1 part of polycarbodiimide (PCDI), 0.1 part -1 part of butyl titanate (TT-01).The present invention is modified PLA/PPA blend as reactive compatibilizer using multifunctionality PCDI and TT-01, and PCDI can improve the high-temperature stability and compatibility of material well, and processing performance can also improve.After adding PCDI, the breaking strength and elasticity modulus of PLA/PPA blend fibers decrease, and elongation at break is significantly improved, and flexibility is improved.The addition of TT-01 promotes the ester exchange reaction between PLA and PPA, to further improve the stability and compatibility of product.
Description
Technical field
The present invention relates to biodegradable technical field of polymer materials, and in particular to arrives a kind of high flexibility polylactic acid
Fibrous composite and preparation method thereof.
Background technique
Polylactic acid/polypropylene glycol adipate (PLA/PPA) fiber has good machine as a kind of novel environment-friendlyfiber fiber
Tool performance, degradability, good biocompatibility and the advantages such as production energy consumption is low, but in certain field, such as
Medicine, packaging and cable coat field, and since PLA/PPA compatibility is bad, the partial properties for causing material are especially soft
The requirement of product is not achieved in property.Herein for these problems, innovative is used as reaction using multi-functional polycarbodiimide
Property expanding material be further modified PLA/PPA blend, the addition of polycarbodiimide (PCDI) can improve blend well
High-temperature stability and compatibility, and the processing performance of blend improves, after adding PCDI, PLA/PPA blend fibers it is disconnected
Resistance to spalling and elasticity modulus decrease, therefore the deformability of blended fiber is significantly improved, and flexibility is improved,
And the addition of butyl titanate has been catalyzed the ester exchange reaction between PLA and PPA, to further improve the compatibility of product
And flexibility.Currently, specializing in for polyester modification PLA fiber softening has not been reported, there is the present invention important research to anticipate
Justice and application value.
Summary of the invention
The present invention provides a kind of high flexibility acid fiber by polylactic composite material and preparation method, the systems of the composite material
Preparation Method is simple and easy, and lactic acid composite material obtained is made to have good flexibility.
The composite wood of acid fiber by polylactic flexibility is improved the purpose of the present invention is preparing a kind of by way of blending and modifying
Material, the parts by weight of each component and component that include are as follows:
70 parts -90 parts of polylactic acid (PLA)
10 parts -30 parts of polypropylene glycol adipate (PPA)
0.1 part -1 part of polycarbodiimide (PCDI)
0.1 part -1 part of butyl titanate (TT-01)
The polylactic acid weight average molecular weight is 80000-150000g/mol.
Described polypropylene glycol adipate (PPA) its weight average molecular weight is 20000-100000g/mol.
A kind of preparation method of high flexibility acid fiber by polylactic composite material of the invention, including polylactic acid and its blending are cut
The preparation step and polylactic acid of piece and its preparation step of blended fiber.
(1) polylactic acid and its blended slice described in are prepared by the following method:
By PLA resin under conditions of 60 DEG C it is vacuum dried for 24 hours, then by 35-45 parts of PLA, 10-30 parts of PPA, 0.1-
1 part of PCDI and 0.1-1 parts of TT-01 is uniformly mixed by a certain percentage, double screw extruder melt blending is added, PLA/ is prepared
PPA/PCDI/TT-01 co-blended spinning slice, wherein extrusion temperature is between 150-180 DEG C.
(2) polylactic acid and its blended fiber described in are prepared by the following method:
By pure 35-45 parts of PLA and step (1) preparation PLA/PPA/PCDI/TT-01 blended slice in vacuum drying oven in
Dry 48h, then prepares fiber by melt spinning-drawing-off two-step method at 90 DEG C.Then it is come into being by spinning machine spinning
Fiber obtains the preliminary draft silk of different winding speeds through winding after oiling.
The spinneret of step (1) described spinning machine is 24 holes, and aperture 0.3mm, spinneret orifice draw ratio (L/D) is 3.
Spinning temperature described in step (2) is between 220-245 DEG C, and drawing temperature is between 80-95 DEG C, heat setting temperature
Between 100-130 DEG C.
Beneficial effects of the present invention:
What the present invention innovated is made using multi-functional polycarbodiimide (PCDI) and butyl titanate (TT-01) combination
For the modified PLA/PPA blend of reactive compatibilizer, the addition of PCDI can improve well the high-temperature stability of blend with
Compatibility, and the processing performance of blend improves, after adding PCDI, the breaking strength and springform of PLA/PPA blend fibers
Amount decreases, therefore the deformability of blended fiber is significantly improved, and flexibility is improved, and blended fiber is anti-
Degradation capability is also improved simultaneously and the addition of TT-01 has been catalyzed ester exchange reaction between PLA and PPA, thus into one
Step improves the compatibility and flexibility of product.
PLA slice granulation is blended with PPA by the present invention, and prepares plasticising PLA fiber by melt spinning.The addition of PPA
It can be effectively improved the brittleness of PLA, with the increase of PPA content, the glass transition temperature of material is reduced, and elongation at break is aobvious
It writes and improves, fracture section is in apparent plastic deformation, but the compatibility poor of material.Therefore the present invention is using multi-functional poly-
Carbodiimides and butyl titanate combination are modified PLA/PPA blend as reactive compatibilizer, and PCDI can be fine
Ground improves the high-temperature stability and compatibility of material, and processing performance can also improve.After adding PCDI, PLA/PPA blend fibers
Breaking strength and elasticity modulus decrease, elongation at break is significantly improved, and flexibility is improved.TT-01's
The ester exchange reaction promoted between PLA and PPA is added, to further improve the stability and compatibility of product.
Specific embodiment
One detailed elaboration is done to the present invention below with reference to specific embodiment.
The present invention relates to a kind of high flexibility acid fiber by polylactic composite materials, according to parts by weight include following components: poly-
70 parts -90 parts of lactic acid (PLA), 10 parts -30 parts of polypropylene glycol adipate (PPA), 0.1 part -1 of polycarbodiimide (PCDI)
Part, 0.1 part -1 part of butyl titanate (TT-01).
In following each examples, the polylactic acid weight average molecular weight is 80000-150000g/mol;It is described to gather oneself two
Acid propylene glycol ester (PPA) its weight average molecular weight is 20000-100000g/mol.
Embodiment 1
80 parts of polylactic acid (PLA), 20 parts of polypropylene glycol adipate (PPA), 0.5 part of polycarbodiimide (PCDI), titanium
Sour 0.5 part of four butyl ester.
(1) blend modified polylactic acid fiber is prepared by the following method: 40 parts of PLA resins are passed through under conditions of 60 DEG C
Vacuum drying for 24 hours, then uniformly mixes/TT-01(0.5 part of/PCDI(0.5 part of/PPA(20 part of PLA (40 parts)))), addition pair
Screw extruder melt blending prepares spinning chips, and extrusion temperature is at 160 DEG C;
(2) preparation of polylactic acid and its blended fiber: by PLA (40 parts)/PPA(20 of 40 parts of PLA and step (1) preparation
Part)/PCDI(0.5 parts)/TT-01(0.5 parts) blended slice dry 48h at 90 DEG C in vacuum drying oven, then pass through melting
Spinning-drawing-off two-step method prepares fiber.Wherein, spinneret is 24 holes, and aperture 0.3mm, spinneret orifice draw ratio (L/D) is 3.So
As-spun fibre is obtained by spinning machine spinning afterwards, obtains the preliminary draft silk of different winding speeds through winding after oiling.Spinning temperature
At 230 DEG C, drawing temperature is at 85 DEG C, and heat setting temperature is at 115 DEG C.
Embodiment 2-4 is identical as 1 preparation step of embodiment and processing conditions, the difference is that the additive amount of each raw material.
Embodiment 2
70 parts of polylactic acid (PLA), 30 parts of polypropylene glycol adipate (PPA), 0.1 part of polycarbodiimide (PCDI), titanium
Sour 0.1 part of four butyl ester.
(1) blend modified polylactic acid fiber is prepared by the following method: 35 parts of PLA resins are passed through under conditions of 60 DEG C
It is dried in vacuo for 24 hours, then by PLA(35 parts)/PPA(30 parts)/PCDI(0.1 parts)/TT-01(0.1 parts) uniformly mixing, it is added double
Screw extruder melt blending prepares spinning chips, and extrusion temperature is at 150 DEG C;
(2) preparation of polylactic acid and its blended fiber: by PLA(35 part of 35 parts of PLA and step (1) preparation)/PPA(30
Part)/PCDI(0.1 parts)/TT-01(0.1 parts) blended slice dry 48h at 90 DEG C in vacuum drying oven, then pass through melting
Spinning-drawing-off two-step method prepares fiber.Wherein, spinneret is 24 holes, and aperture 0.3mm, spinneret orifice draw ratio (L/D) is 3.So
As-spun fibre is obtained by spinning machine spinning afterwards, obtains the preliminary draft silk of different winding speeds through winding after oiling.Spinning temperature
At 220 DEG C, drawing temperature is at 80 DEG C, and heat setting temperature is at 100 DEG C.
Embodiment 3
90 parts of polylactic acid (PLA), 10 parts of polypropylene glycol adipate (PPA), 1 part of polycarbodiimide (PCDI), metatitanic acid
Four 1 part of butyl esters.
(1) blend modified polylactic acid fiber is prepared by the following method: 45 parts of PLA resins are passed through under conditions of 60 DEG C
It is dried in vacuo for 24 hours, then by PLA(45 parts)/PPA(10 parts)/PCDI(1 parts)/TT-01(1 parts) uniformly mixing, twin-screw is added
Extruder melt blending prepares spinning chips, and extrusion temperature is at 180 DEG C;
(2) preparation of polylactic acid and its blended fiber: by PLA(45 part of 45 parts of PLA and step (1) preparation)/PPA(10
Part)/PCDI(1 parts)/TT-01(1 parts) blended slice dry 48h at 90 DEG C in vacuum drying oven, then pass through melt spinning-
Drawing-off two-step method prepares fiber.Wherein, spinneret is 24 holes, and aperture 0.3mm, spinneret orifice draw ratio (L/D) is 3.Then lead to
It crosses spinning machine spinning and obtains as-spun fibre, obtain the preliminary draft silk of different winding speeds through winding after oiling.Spinning temperature is 245
DEG C, drawing temperature is at 95 DEG C, and heat setting temperature is at 130 DEG C.
Embodiment 4
90 parts of polylactic acid (PLA), 10 parts of polypropylene glycol adipate (PPA), 0.5 part of polycarbodiimide (PCDI), titanium
Sour 0.2 part of four butyl ester
(1) blend modified polylactic acid fiber is prepared by the following method: 45 parts of PLA resins are passed through under conditions of 60 DEG C
It is dried in vacuo for 24 hours, then by PLA(45 parts)/PPA(10 parts)/PCDI(0.5 parts)/TT-01(0.5 parts) uniformly mixing, it is added double
Screw extruder melt blending prepares spinning chips, and extrusion temperature is at 150 DEG C;
(2) preparation of polylactic acid and its blended fiber: by PLA(45 part of 45 parts of PLA and step (1) preparation)/PPA(10
Part)/PCDI(0.5 parts)/TT-01(0.5 parts) blended slice dry 48h at 90 DEG C in vacuum drying oven, then pass through melting
Spinning-drawing-off two-step method prepares fiber.Wherein, spinneret is 24 holes, and aperture 0.3mm, spinneret orifice draw ratio (L/D) is 3.So
As-spun fibre is obtained by spinning machine spinning afterwards, obtains the preliminary draft silk of different winding speeds through winding after oiling.Spinning temperature
At 230 DEG C, drawing temperature is at 85 DEG C, and heat setting temperature is at 115 DEG C.
90 parts of 1 polylactic acid of comparative example (PLA), 10 parts of polypropylene glycol adipate (PPA)
Blend modified polylactic acid fiber is prepared by the following method: by 45 parts of PLA resins through true under conditions of 60 DEG C
Sky is dry for 24 hours, and then by/PPA(10 part of PLA (45 parts)) uniformly mixing, the preparation spinning of double screw extruder melt blending is added
Slice, extrusion temperature is at 160 DEG C.By 45 parts of PLA and/PPA(10 parts of PLA (45 parts)) blended slice in 90 DEG C in vacuum drying oven
Then lower dry 48h prepares fiber by melt spinning-drawing-off two-step method.Wherein, spinneret be 24 holes, aperture 0.3mm,
Spinneret orifice draw ratio (L/D) is 3.Then as-spun fibre is obtained by spinning machine spinning, obtains different windings through winding after oiling
The preliminary draft silk of speed.Spinning temperature is at 230 DEG C, and drawing temperature is at 85 DEG C, and heat setting temperature is at 115 DEG C.
Performance test:
Batten is made in above-mentioned implementation 1-4 and comparative example 1 composite fiber prepared, with XQ-1 fiber strength and elongation instrument root
It is tested according to standard ISO 527-1:2012, ISO527-2:2012 and ISO178:2010, test clamp distance is 10mm, is broken
Split speed be 20mm/min, test data such as the following table 1:
Table 1
Test item | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
Tensile strength | MPa | 2.9 | 3.2 | 3.3 | 3.5 | 7.8 |
Elasticity modulus | MPa | 33.2 | 44.3 | 45.6 | 38.1 | 82 |
Elongation at break | % | 280 | 300 | 350 | 272 | 18.7 |
Data show the mechanical property of PLA/PPA and PLA/PPA/PCDI/TT-01 blended fiber.It is blended with PLA/PPA
Fiber is compared, and addition PCDI and TT-01 is not improved the mechanical property of blended fiber, the tensile strength and elasticity modulus of material
Decline.This may be because the flexibility of macromolecular increases after addition PCDI, fiber can drafting multiple also become larger,
Maximum drafting multiple can reach 20 times or so.Therefore PCDI and TT-01 addition can improve well blend high temperature it is steady
Qualitative and compatibility, deformability and surface flatness are significantly improved, and flexibility is improved.
Claims (2)
1. a kind of high flexibility acid fiber by polylactic composite material, it is characterised in that: the parts by weight of each component and component that include
Number is as follows:
70 parts -90 parts of polylactic acid
10 parts -30 parts of polypropylene glycol adipate
0.1 part -1 part of polycarbodiimide
0.1 part -1 part of butyl titanate;
The polylactic acid weight average molecular weight is 80000-150000g/mol;
The polypropylene glycol adipate weight average molecular weight is 20000-100000g/mol;
The preparation method of the high flexibility acid fiber by polylactic composite material, the preparation step including polylactic acid and its blended slice
Rapid and polylactic acid and its blended fiber preparation step;
(1) the polylactic acid blend slice is prepared by the following method:
By polylactic acid under conditions of 60 DEG C it is vacuum dried for 24 hours, then by after drying 35-45 part polylactic acid, 10-30 parts it is poly-
Adipic acid propylene glycol ester, 0.1-1 part polycarbodiimide and 0.1-1 parts of butyl titanates uniformly mix in proportion, and double spiral shells are added
Bar extruder melt blending is prepared polylactic acid/polypropylene glycol adipate/polycarbodiimide/butyl titanate and spinning is blended
Silk slice, extrusion temperature is between 150-180 DEG C;
(2) polylactic acid blend fiber is prepared by the following method:
By polylactic acid/polypropylene glycol adipate/polycarbodiimide/metatitanic acid four of 35-45 parts of polylactic acid and step (1) preparation
Butyl ester co-blended spinning slice dry 48h at 90 DEG C in vacuum drying oven, then obtains as-spun fibre by spinning machine spinning, on
The preliminary draft silk of different winding speeds is obtained through winding after oil;
The spinning temperature is between 220-245 DEG C, and drawing temperature is between 80-95 DEG C, and heat setting temperature is at 100-130 DEG C
Between.
2. high flexibility acid fiber by polylactic composite material according to claim 1, it is characterised in that: step (2) described spinning
The spinneret of silk machine is 24 holes, and aperture 0.3mm, spinneret orifice draw ratio (L/D) is 3.
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CN109853084B (en) * | 2018-12-29 | 2021-06-11 | 恒天纤维集团有限公司 | Polylactic acid/polyester elastomer composite elastic fiber and preparation method thereof |
CN110144639B (en) * | 2019-06-06 | 2021-11-09 | 东华大学 | Soft and hydrolysis-resistant polylactic acid fiber and preparation method thereof |
CN111572983B (en) * | 2020-04-26 | 2022-04-05 | 浙江天益塑业有限公司 | Preparation method of high-strength degradable paper-plastic composite bag |
CN112410929A (en) * | 2020-11-03 | 2021-02-26 | 南通大学 | PLA/PTMC biomass composite fiber and preparation method and application thereof |
CN115948815B (en) * | 2022-11-18 | 2023-07-21 | 湖北博韬合纤有限公司 | Preparation method of PLA degradable short fiber |
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CN101838448A (en) * | 2009-03-18 | 2010-09-22 | 东丽纤维研究所(中国)有限公司 | Blended resin combination and moldings thereof |
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