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 PDFInfo
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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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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000009987 spinning Methods 0.000 title claims abstract description 55
- 239000004310 lactic acid Substances 0.000 title claims abstract description 35
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title description 4
- 239000004626 polylactic acid Substances 0.000 claims abstract description 27
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000008188 pellet Substances 0.000 claims description 28
- 229920000728 polyester Polymers 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000005453 pelletization Methods 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000002667 nucleating agent Substances 0.000 claims description 6
- -1 acryl Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 210000000481 breast Anatomy 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229920003163 Eudragit® NE 30 D Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims 2
- 229920006243 acrylic copolymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract 1
- 239000012779 reinforcing material Substances 0.000 abstract 1
- 230000002596 correlated effect Effects 0.000 description 9
- 150000002118 epoxides Chemical class 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 235000012241 calcium silicate Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical class OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- BFSPAPKTIGPYOV-BQYQJAHWSA-N (e)-1-[4-(4-hydroxyphenyl)piperazin-1-yl]-3-thiophen-2-ylprop-2-en-1-one Chemical compound C1=CC(O)=CC=C1N1CCN(C(=O)\C=C\C=2SC=CC=2)CC1 BFSPAPKTIGPYOV-BQYQJAHWSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HDKNIIWKWHFLIC-UHFFFAOYSA-N C(C)OC(C=C)=O.C1=CC=CC=C1 Chemical compound C(C)OC(C=C)=O.C1=CC=CC=C1 HDKNIIWKWHFLIC-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N glycerine triacetate Natural products CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ITJNARMNRKSWTA-UHFFFAOYSA-N nisoxetine Chemical compound C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1OC ITJNARMNRKSWTA-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- 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
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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