CN106633709B - A kind of spinning high-temperature resistant lactic acid composite material and preparation method thereof - Google Patents

A kind of spinning high-temperature resistant lactic acid composite material and preparation method thereof Download PDF

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CN106633709B
CN106633709B CN201610841062.4A CN201610841062A CN106633709B CN 106633709 B CN106633709 B CN 106633709B CN 201610841062 A CN201610841062 A CN 201610841062A CN 106633709 B CN106633709 B CN 106633709B
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composite material
acid
spinning
temperature
lactic acid
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CN106633709A (en
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白永平
李卫东
王成乐
李晶波
席丹
殷晓芬
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Shenzhen Huayuan new material Co., Ltd.
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Wuxi Haite New Material Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/12Applications used for fibers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Biological Depolymerization Polymers (AREA)

Abstract

The present invention designs a kind of spinning high-temperature resistant lactic acid composite material, and the composite material is by including that following raw material is made:Polylactic acid 40~60wt% of the crystallization temperature at 150~200 DEG C, crystallization temperature is in 100~140 DEG C of 25~45wt% of polylactic acid, 1~15wt% of acrylic polymer, 1~5wt% of tackifier.Present invention employs 100~140 DEG C of polylactic acid of 150~200 DEG C of polylactic acid of crystallization temperature and crystallization temperature to be compounded, it is aided with the cementability that acrylic polymer and tackifier reach the shrinking percentage after the mutually temperature tolerance of collaboration reinforcing material, reduction spinning, improve spinning again, there are safe and non-toxic, reserved materials biodegradability to greatest extent excellent properties.Processing method of the present invention is simple, is conducive to the efficient industrialized production of material.

Description

A kind of spinning high-temperature resistant lactic acid composite material and preparation method thereof
Technical field
The invention belongs to polymeric material field, the present invention relates to a kind of spinning high-temperature resistant lactic acid composite material and its Preparation method.
Background technology
With the development in the world, fossil resource is increasingly constantly being consumed, however the fossil resources such as oil and coal are Non-renewable resources, the mankind are gradually being faced with the reality of fossil resource exhaustion.Numerous with oil etc. is the macromolecule of raw material Material will also be faced with huge challenge;These for example poly- second of high molecular material being widely used dependent on oil simultaneously Alkene, polypropylene, polystyrene etc. also bring serious environmental pollution i.e. " white pollution ";Further more, the environmental consciousness of people by It is cumulative strong, can the renewable biodegradable material that can be recycled increasingly be taken seriously.
Polylactic acid(PLA)It is a kind of renewable biodegradable environmental-friendly novel-section material that can be recycled, it gathers It is lactic acid monomer to close raw material, and lactic acid is to ferment to obtain from the reproducible starch crops such as corn, cassava, sugarcane.Polylactic acid Carbon dioxide and water are only generated in common biodegradable such as compost degradation process, it is free from environmental pollution not consume high-energy source also not Carbon dioxide is extraly generated, reaches with the photosynthesis absorbing carbon dioxide of the vegetation such as crops and recycles renewable profit With.With other it is renewable it is biodegradable material can be recycled compared with, poly-lactic acid material has many advantages, such as high intensity, high-modulus Be conducive to the application of material.
It has widely been studied based on the above advantage polylactic acid, Chinese patent CN103819884A adds inorganic nano material Material is prepared by reactive extrursion equipment with certain durothermic polylactic acid master batch with lactic acid monomer or prepolymer, then with poly- breast The material of heat-resisting high toughening is made in acid compounding;Chinese patent CN03149911.2 improves polylactic acid by adding inorganic filler micro mist Heat resistance;Chinese patent 200610037894.7, the patents such as CN102492273A disclose natural fiber and synthetic fibers with The composite material of polylactic acid obtains the lactic acid composite material of heat resistant type.With first-class patent by adding a large amount of nanometer materials Material, inorganic filler micro mist and fiber can obtain the lactic acid composite material with good heat resistance energy, but for spinning work For skill, the addition of these materials is easy to block the easily series such as fracture of wire in spinning equipment even damage equipment and drawing process and asks Topic.It has been proposed the polylactic acid commercially produced product of each veriety at present, wherein it is no lack of the polylactic acid commodity of some high-temperature resistants, but Be this kind of poly-lactic acid material it is the crystalline rate and knot that material in process is for example improved by improving the crystallinity of itself Brilliant degree achievees the purpose that high-temperature resistant, this results in the cementability after melt spinning between silk and silk to reduce and the contraction of spinning Rate is larger.Chinese patent CN101735582A carries out compounding using polymethyl methacrylate and polylactic acid and squeezes out the obtained transparency Good polylactic acid/composite material of polymethyl methacrylate with certain heat resistance, but to improve composite material Temperature tolerance needs to add heat stabilizer, and the additive amount of polymethyl methacrylate will reach 30wt% or more, great shadow The degradation property of material is rung;And it is added to maleic anhydride noxious material in process, it is unfavorable for the food of material Product safety.So a kind of nontoxic lactic acid composite material of new type of safe is an important research direction.
Invention content
In view of the above problems, we have proposed new spinning high-temperature resistant type lactic acid composite material and relevant preparations Method.It uses crystallization temperature and in 150~200 DEG C and 100~140 DEG C of polylactic acid compound respectively and reach mutually collaboration increasing Adhesive property after strong heatproof effect and spinning, and assist, with acrylic polymer and tackifier, the composite material being made to have High temperature tolerance, keeps the advantages that material biological degradability and good spinning cementability at low-shrinkage to greatest extent.
To complete object above, the present invention uses following technical scheme:
A kind of spinning high-temperature resistant lactic acid composite material, by including that following raw material is made:
Polylactic acid 40~60wt% of the crystallization temperature at 150~200 DEG C, polylactic acid 25 of the crystallization temperature at 100~140 DEG C ~45wt%, 1~15wt% of acrylic polymer, 1~5wt% of tackifier.
Preferably, the crystallization temperature preferentially selects 6202D and SUPLA751 in 150~200 DEG C of polylactic acid.
Preferably, the crystallization temperature preferentially selects 6302D in 100~140 DEG C of polylactic acid.
Preferably, the acrylic polymer includes polyacrylic acid, polyacrylate, polymethylacrylic acid, propylene Acid-methacrylic acid copolymer, acryl acid-methyl methacrylate copolymer, acrylic-styrene copolymer, acrylic acid first Ester-styrol copolymer, methyl acrylate-methylmethacrylate copolymer, ethacrylate-styrene copolymer, propylene Acetoacetic ester-methacrylic acid copolymer, EUDRAGIT NE 30 D etc..
Preferably, the tackifier are at least one of solid epoxy, terminal carboxyl polyester, hydroxyl telechelic polyester.
The terminal carboxyl polyester includes hyperbranched terminal carboxyl polyester, and the hydroxyl telechelic polyester includes hyperbranched terminal hydroxy group Polyester.
Preferably, the raw material of the composite material further includes 0.1~1wt% of nucleating agent, 0.1~1wt% of antioxidant.
Preferably, the nucleating agent is inorganic nano material, preferentially selects nano silicate(Such as nanometer sodium metasilicate, receive Rice alumina silicate, nanometer calcium silicates etc.), nano silicon dioxide.
Preferably, the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls)Propionic acid] pentaerythritol ester(It is anti- Oxygen agent 1010), bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) calcium(Antioxidant 1425)Deng.
The method for preparing above-mentioned composite material, including:After mixing by each raw material, it is squeezed at 170~210 DEG C Go out to be granulated, dry 8~10h under 40~60 DEG C of vacuum conditions;Then by pellet in 100~130 DEG C of pre-crystallized 2~4h, then 120~165 DEG C carry out 2~4h of solid-phase tack producing to get to the composite material;
Alternatively, after mixing by each raw material, the extruding pelletization at 170~210 DEG C, in 40~60 DEG C of vacuum items Dry 8~10h is to get to the composite material under part.
The outstanding feature of the present invention is with advantage:
1, the present invention, which has selected, has high glass-transition temperature(Tg)Acrylic polymer, can be very good to improve The temperature tolerance of lactic acid composite material, and reduce the spinning shrinking percentage of composite material.
2, the present invention considerably reduces the additive amount of non-biodegradable material, remains the biology of material to greatest extent Degradation property further reduces pollution of the material to environment.
3, the present invention is by adding tackifier simultaneously(Or)It can be reduced by solid-phase tack producing reaction because process makes poly- breast Sour material degradation and cause serious viscosity to drop, significantly improve the temperature tolerance of material.
4, the nucleating agent that the present invention adds can be effectively promoted rapid crystallization in material forming process, further increase resistance to Warm nature energy.
5, the complex material and auxiliary agent that the present invention uses do not have toxicity, are not influenced on process, will not be set to processing It is standby to generate damage, it is a kind of biodegradable nontoxic safety composite material.
6, the processing flow that the present invention uses is simple, and equipment requirement is low, and production efficiency is higher, easily realizes efficient industry Production.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Unless otherwise instructed, the number of each raw material is parts by weight in the embodiment of the present invention.
Embodiment 1
60 parts of 6202D are dried into 8h, 30 parts of 6302D and 5 part of polyacrylic acid, 60 DEG C of vacuum conditions under 100 DEG C of vacuum conditions After small dry 10h, 5 parts of terminal carboxyl polyesters are added(Molecular weight 800~8000), 0.3 part of antioxidant 1010,0.5 part of Nano-meter SiO_22, It is uniformly mixed at room temperature, double-screw extruding pelletizing at a temperature of 170~210 DEG C, dry 8 under 40~60 DEG C of vacuum conditions ~10h;Then by pellet in 100~130 DEG C of pre-crystallized 2~4h, carried out at 120~165 DEG C 2~4h of solid-phase tack producing to get to Spinning high-temperature resistant lactic acid composite material pellet.By composite material pellet at a temperature of 170~210 DEG C by spinning equipment into To get to high-temperature resistant lactic acid composite material spun articles, correlated performance is listed in table 1 for row spinning.
Embodiment 2
By 50 parts of 6202D, dry 8h, 30 parts of 60 DEG C of 6302D and 15 part of polymethylacrylic acid are true under 100 DEG C of vacuum conditions Under empty condition after dry 10h, 5 parts of terminal carboxyl polyesters are added(Molecular weight 800~8000), 0.3 part of antioxidant 1010,0.5 part receive Rice SiO2, it is uniformly mixed at room temperature, double-screw extruding pelletizing at a temperature of 170~210 DEG C, in 40~60 DEG C of vacuum conditions 8~10h of lower drying;Then by pellet in 100~130 DEG C of pre-crystallized 2~4h, 2~4h of solid-phase tack producing is carried out at 120~165 DEG C, Obtain spinning high-temperature resistant lactic acid composite material pellet.Composite material pellet is passed through into spinning at a temperature of 170~210 DEG C Equipment carries out spinning to get to high-temperature resistant lactic acid composite material spun articles, and correlated performance is listed in table 1.
Embodiment 3
By 60 parts of 6202D, dry 8h, 30 parts of 6302D and 5 part of acrylic acid-methacrylic acids are total under 100 DEG C of vacuum conditions After the small dry 10h of 60 DEG C of vacuum conditions of polymers, 5 parts of solid epoxies are added(Epoxide equivalent 200~950), 0.3 part of antioxidant 1010,0.5 part of nanometer sodium metasilicate, is uniformly mixed at room temperature, double-screw extruding pelletizing at a temperature of 170~210 DEG C, 40 Dry 8~10h is to get to spinning high-temperature resistant lactic acid composite material pellet under~60 DEG C of vacuum conditions.By composite material grain Material carries out spinning to get to high-temperature resistant lactic acid composite material spun articles at a temperature of 190~210 DEG C by spinning equipment, Correlated performance is listed in table 1.
Embodiment 4
60 parts of SUPLA751 are dried into 8h, 30 parts of 6302D and 5 part of acrylate-styrenes under 100 DEG C of vacuum conditions After the small dry 10h of 60 DEG C of vacuum conditions of copolymer, 5 parts of end carboxyl super branched polyester are added(Molecular weight 1000~10000)、0.3 Part antioxidant 1010,0.5 part of Nano-meter SiO_22, it is uniformly mixed, is made with twin-screw extrusion at a temperature of 170~210 DEG C at room temperature Grain, dry 8~10h under 40~60 DEG C of vacuum conditions;Then by pellet in 100~130 DEG C of pre-crystallized 2~4h, 120~ 165 DEG C carry out 2~4h of solid-phase tack producing to get to spinning high-temperature resistant lactic acid composite material pellet.Composite material pellet is existed Spinning is carried out to get to high-temperature resistant lactic acid composite material spun articles by spinning equipment at a temperature of 170~210 DEG C, it is related Performance is listed in table 1.
Embodiment 5
55 parts of 6202D are dried into 8h, 30 parts of 6302D and 10 part of ethyl acrylate-metering systems under 100 DEG C of vacuum conditions After the small dry 10h of 60 DEG C of vacuum conditions of acid copolymer, 5 parts of hydroxyl telechelic polyesters are added(Molecular weight 500~10000), 0.3 part of antioxygen 1010,0.5 parts of Nano-meter SiO_2s of agent2, it is uniformly mixed at room temperature, double-screw extruding pelletizing at a temperature of 170~210 DEG C, 40 Dry 8~10h under~60 DEG C of vacuum conditions;Then it by pellet in 100~130 DEG C of pre-crystallized 2~4h, is carried out at 120~165 DEG C 2~4h of solid-phase tack producing is to get to spinning high-temperature resistant lactic acid composite material pellet.By composite material pellet at 170~210 DEG C At a temperature of spinning carried out to get to high-temperature resistant lactic acid composite material spun articles by spinning equipment, correlated performance is listed in table 1。
Embodiment 6
50 parts of 6202D are dried into 8h, 35 parts of 6302D and 10 part of acrylic acid-methacrylic acid first under 100 DEG C of vacuum conditions After the small dry 10h of 60 DEG C of vacuum conditions of ester copolymer, 5 parts of solid epoxies are added(Epoxide equivalent 200~950), 0.3 part it is anti- 1010,0.5 parts of nanometer aluminium silicates of oxygen agent, are uniformly mixed, double-screw extruding pelletizing at a temperature of 170~210 DEG C at room temperature, Dry 8~10h is to get to spinning high-temperature resistant lactic acid composite material pellet under 40~60 DEG C of vacuum conditions.By composite wood Expect that pellet carries out spinning to get to high-temperature resistant lactic acid composite material spinning system at a temperature of 170~210 DEG C by spinning equipment Product, correlated performance are listed in table 1.
Embodiment 7
50 parts of SUPLA751 are dried into 8h, 35 parts of 6302D and 10 part of ethyl acrylate-methyl under 100 DEG C of vacuum conditions After the small dry 10h of 60 DEG C of vacuum conditions of methyl acrylate copolymer, 5 parts of solid epoxies are added(Epoxide equivalent 200~ 950), 0.3 part of antioxidant 1010,0.5 part of nanometer calcium silicates, be uniformly mixed at room temperature, with double at a temperature of 170~210 DEG C Screw Extrusion is granulated, and dry 8~10h is to get to spinning high-temperature resistant lactic acid composite material under 40~60 DEG C of vacuum conditions Pellet.Composite material pellet is subjected to spinning to get to high-temperature resistant polylactic acid at a temperature of 170~210 DEG C by spinning equipment Composite material spun articles, correlated performance are listed in table 1.
Embodiment 8
By 45 parts of SUPLA751, dry 8h, 35 parts of 6302D and 15 part of acrylicstyrenes are total under 100 DEG C of vacuum conditions After the small dry 10h of 60 DEG C of vacuum conditions of polymers, 5 parts of solid epoxies are added(Epoxide equivalent 200~950), 0.3 part of antioxidant 1010,0.5 part of Nano-meter SiO_22, it is uniformly mixed at room temperature, double-screw extruding pelletizing at a temperature of 170~210 DEG C, 40~ Dry 8~10h is to get to spinning high-temperature resistant lactic acid composite material pellet under 60 DEG C of vacuum conditions.By composite material pellet Spinning is carried out to get to high-temperature resistant lactic acid composite material spun articles, phase by spinning equipment at a temperature of 170~210 DEG C It closes performance and is listed in table 1.
Embodiment 9
50 parts of 6202D are dried into 8h, 35 parts of 6302D and 10 part of methyl acrylate-metering systems under 100 DEG C of vacuum conditions After the small dry 10h of 60 DEG C of vacuum conditions of sour methyl terpolymer, 2.5 parts of solid epoxies are added(Epoxide equivalent 200~950)、 2.5 parts of terminal carboxyl polyesters(Molecular weight 800~8000), 0.3 portion of antioxidant 1010,0.5 portion of nucleating agent, mixing is equal at room temperature Even, double-screw extruding pelletizing at a temperature of 170~210 DEG C, dry 8~10h is to get to spinning under 40~60 DEG C of vacuum conditions Silk high-temperature resistant lactic acid composite material pellet.Composite material pellet is carried out at a temperature of 170~210 DEG C by spinning equipment To get to high-temperature resistant lactic acid composite material spun articles, correlated performance is listed in table 1 for spinning.
Embodiment 10
55 parts of SUPLA751 are dried into 8h, 30 parts of 6302D and 10 part of ethyl acrylate-benzene second under 100 DEG C of vacuum conditions After the small dry 10h of 60 DEG C of vacuum conditions of alkene copolymer, 5 parts of solid epoxies are added(Epoxide equivalent 200~950), 0.3 part it is anti- 1010,0.5 parts of nanometer calcium silicates of oxygen agent, are uniformly mixed, double-screw extruding pelletizing at a temperature of 170~210 DEG C at room temperature, Dry 8~10h is to get to spinning high-temperature resistant lactic acid composite material pellet under 40~60 DEG C of vacuum conditions.By composite wood Expect that pellet carries out spinning to get to high-temperature resistant lactic acid composite material spinning system at a temperature of 170~210 DEG C by spinning equipment Product, correlated performance are listed in table 1.
Embodiment 11
45 parts of 6202D are dried into 8h, 35 parts of 6302D and 15 part of Sodium Polyacrylates, 60 DEG C of vacuum under 100 DEG C of vacuum conditions After the small dry 10h of condition, 5 parts of solid epoxies are added(Epoxide equivalent 200~950), 0.3 part of antioxidant 1010,0.5 part receive Rice SiO2, it is uniformly mixed at room temperature, double-screw extruding pelletizing at a temperature of 170~210 DEG C, in 40~60 DEG C of vacuum conditions 8~10h of lower drying;Then by pellet in 100~130 DEG C of pre-crystallized 2~4h, 2~4h of solid-phase tack producing is carried out at 120~165 DEG C, Obtain spinning high-temperature resistant lactic acid composite material pellet.Composite material pellet is passed through into spinning at a temperature of 170~210 DEG C Equipment carries out spinning to get to high-temperature resistant lactic acid composite material spun articles, and correlated performance is listed in table 1.
Tg and shrinking percentage after 1 embodiment of table, 1~11 composite material spinning with comparison example
Whether spinning, which is bonded test method, in table is coated between silk surface examination silk and silk with triacetyl glycerine Bonding.
From the point of view of data in table, gained poly lactic acid in use for spinning composite material Tg can be made than pure by the design of different formulations The Tg of polylactic acid improves 10 DEG C or more the temperature tolerances for substantially increasing material;With the addition of acrylic polymer, spinning Shrinking percentage has apparent reduction;The compound cementability that can be very good to improve spinning of two kinds of polylactic acid.Gained production indicated above The needs that product can meet industrial production completely and life uses.
The 6202D of the present invention(LLC IngeoTM Biopolymer)And 6302D(LLC IngeoTM Biopolymer) Purchased from NatureWorks, SUPLA751 purchased from Taiwan permit friend at.
Examples detailed above is not limited only to make those skilled in the art understand and apply the invention This.Expert in the art, scholar and long campaigns those skilled in the art can be easy to make modification to the present invention, and The spirit of the invention is applied in other examples.Therefore, the present invention is not limited to cited certain embodiments, every to this What invention general principle carried out simple modifications and modification all should be within protection scope of the present invention.

Claims (9)

1. a kind of spinning high-temperature resistant lactic acid composite material, which is characterized in that the composite material is by including following raw material system At:
Polylactic acid 40~60wt% of the crystallization temperature at 150~200 DEG C, crystallization temperature 100~140 DEG C polylactic acid 25~ 45wt%, 1~15wt% of acrylic polymer, 1~5wt% of tackifier, 0.1~1wt% of nucleating agent;
The acrylic polymer includes polyacrylic acid, polyacrylate, polymethylacrylic acid, acrylic acid-metering system Acid copolymer, acryl acid-methyl methacrylate copolymer, acrylic-styrene copolymer, acrylate-styrene are total Polymers, methyl acrylate-methylmethacrylate copolymer, ethacrylate-styrene copolymer, ethyl acrylate-methyl Acrylic copolymer, EUDRAGIT NE 30 D;
The tackifier are at least one of solid epoxy, terminal carboxyl polyester, hydroxyl telechelic polyester.
2. composite material according to claim 1, which is characterized in that poly- breast of the crystallization temperature at 150~200 DEG C Acid selects 6202D and SUPLA751.
3. composite material according to claim 1, which is characterized in that poly- breast of the crystallization temperature at 100~140 DEG C Acid selects 6302D.
4. composite material according to claim 1, which is characterized in that the terminal carboxyl polyester includes hyperbranched end carboxyl Polyester, the hydroxyl telechelic polyester include hyperbranched hydroxyl telechelic polyester.
5. composite material according to claim 1, which is characterized in that the raw material includes 0.1~1wt% of antioxidant.
6. composite material according to claim 5, which is characterized in that the antioxidant is four [β-(3,5- bis- tertiary fourths Base -4- hydroxy phenyls)Propionic acid] pentaerythritol ester and/or bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) calcium.
7. composite material according to claim 1, which is characterized in that the nucleating agent is inorganic nano material.
8. composite material according to claim 7, which is characterized in that the inorganic nano material selection nano silicate, Nano silicon dioxide.
9. a kind of method preparing any composite materials of claim 1-8, which is characterized in that including:By each original Expect after mixing, the extruding pelletization at 170~210 DEG C, dry 8~10h under 40~60 DEG C of vacuum conditions;Then by pellet 2~4h of solid-phase tack producing is carried out to get to the composite material in 100~130 DEG C of pre-crystallized 2~4h, then at 120~165 DEG C;
Alternatively, after mixing by each raw material, the extruding pelletization at 170~210 DEG C, under 40~60 DEG C of vacuum conditions Dry 8~10h is to get to the composite material.
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CN110305435B (en) * 2019-07-31 2022-01-25 金旸(厦门)新材料科技有限公司 Transparent toughened polylactic acid/acrylic alloy material and preparation raw materials and preparation method thereof
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