CN103131149A - Polylactic acid composite material, preparation method thereof and application thereof - Google Patents
Polylactic acid composite material, preparation method thereof and application thereof Download PDFInfo
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- CN103131149A CN103131149A CN2013100415749A CN201310041574A CN103131149A CN 103131149 A CN103131149 A CN 103131149A CN 2013100415749 A CN2013100415749 A CN 2013100415749A CN 201310041574 A CN201310041574 A CN 201310041574A CN 103131149 A CN103131149 A CN 103131149A
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- composite material
- lactic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention provides a polylactic acid composite material, a preparation method of the polylactic acid composite material and application of the polylactic acid composite material. The main components of the polylactic acid composite material comprises, by weight, 30-60 parts of polylactic acid, 5-10 parts of oligomeric protein copolymer, 5-20 parts of biodegradable polyester, 0.1-5 parts phosphate containing aromatic group, 5-20 parts of talcum powder, 5-20 parts of fibers, 0.1-1 part of coupling agent, and 0.1-1 part of lubricating agent. The oligomeric protein copolymer is the copolymer of amino acid and lactide. Weight-average molecular weight of the oligomeric protein copolymer is less than ten thousand. According to the polylactic acid composite material, the oligomeric protein copolymer is added into the raw material of the polylactic acid composite material, heat resistance of the polylactic acid composite material is improved, compatibility of the obtained material is good, and mechanical property of the obtained material is good.
Description
Technical field
The present invention relates to for polymeric material field, particularly a kind of heat-proof polylactic acid matrix material, its goods preparation method and application thereof.
Background technology
General-purpose plastics is widely used in every field because of its excellent combination property, is listed as four large support material with iron and steel, timber, cement, and a year usage quantity constantly rises.General-purpose plastics such as polyethylene (PE), polypropylene (PP) and polystyrene (PS) etc. can steady in a long-termly exist at nature, and hard degradation therefore its discarded being difficult to afterwards recycles, has caused serious pollution to environment.Biodegradable plastic can comparatively fast be degraded under physical environment because of it becomes one of effective way that solves the plastic refuse problem of environmental pollution, thereby has caused showing great attention to of people, and biodegradable plastic is competitively developed in countries in the world.
" white pollution " problem that causes for solving waste plastic, each state has all proposed many practical way, and wherein the most effective is also that method uses biodegradable polymeric material to replace the oil synthetic polymeric material exactly the most thoroughly.Compare with the oil synthetic polymeric material, biodegradable polymeric material produces less heat when incinerating, and can keep natural degradation and resynthesis circulation, thereby can not comprise the ecological harmful effect that produces to global environment.And in numerous biodegradable polymeric materials, poly(lactic acid) is considered to most possibly replace the biomaterial of oil synthetic polymeric material due to fully biodegradable and plant origin.But pure poly-lactic acid material and existing lactic acid composite material, its second-order transition temperature is lower, and degree of crystallinity is not high, and finishing time is long in the course of processing, and the mechanical property performance is bad, is unfavorable for widespread use.
Summary of the invention
In sum, the present invention is necessary to provide a kind of good lactic acid composite material of mechanical property of heat resistant type.
Further, also be necessary to provide a kind of preparation method of above-mentioned lactic acid composite material goods.
Further, also be necessary to provide a kind of application of above-mentioned lactic acid composite material.
A kind of lactic acid composite material, its main component is for comprising by weight:
Poly(lactic acid) 30-60 part;
Oligomeric protein multipolymer 5-10 part;
Biodegradable polyester 5-20 part;
Nucleator 0.1-5 part;
Talcum powder 5-20 part;
Fiber 5-20 part;
Coupling agent 0.1-1 part;
Lubricant 0.1-1 part;
Wherein, described oligomeric protein multipolymer is the multipolymer of amino acid and rac-Lactide, and the weight-average molecular weight of described oligomeric protein multipolymer is less than or equal to 10,000.
A kind of lactic acid composite material, by following composition for forming by weight:
Poly(lactic acid) 30-60 part;
Oligomeric protein multipolymer 5-10 part;
Biodegradable polyester 5-20 part;
Nucleator 0.1-5 part;
Talcum powder 5-20 part;
Fiber 5-20 part;
Coupling agent 0.1-1 part;
Lubricant 0.1-1 part;
Wherein, above-mentioned lactic acid composite material, its main component is for comprising by weight:
Poly(lactic acid) 40-50 part;
Oligomeric protein multipolymer 5-10 part;
Biodegradable polyester 15-20 part;
Nucleator 0.1-2 part;
Talcum powder 10-20 part;
Fiber 10-20 part;
Coupling agent 0.2-0.5 part;
Lubricant 0.2-0.5 part.
Wherein, the weight-average molecular weight of described poly(lactic acid) can be 6-20 ten thousand, wherein, poly-in described poly(lactic acid)-D lactic acid content is lower than 5wt%, and the inventor finds by great many of experiments, when poly--D lactic acid content during lower than 5wt%, the resistance toheat of described lactic acid composite material is better, and mechanical property is higher.
Wherein, described amino acid can be selected from any one or more in amino-succinic acid, α-aminopropionic acid, β-alanine, butyrine, beta-aminobutyric acid, γ-aminobutyric acid.
Wherein, the amino acid of described preparation oligomeric protein multipolymer can be (5-20) with the ratio of the molar weight of rac-Lactide: (80-95).
Wherein, described Biodegradable polyester can be selected from the multipolymer of multipolymer, hydroxybutyric acid and the hydroxycaproic acid of poly butylene succinate, poly--3-hydroxybutyrate ester, 3-hydroxybutyrate and 3-hydroxypentanoic acid, one or more mixtures in succinic acid/mutual-phenenyl two acid bromide two alcohol ester.
Wherein, described nucleator preferably contains the phosphoric acid salt of aromatic group, the phosphoric acid salt and the oligomeric protein multipolymer synergy that contain aromatic group, can effectively improve lactic acid composite material of the present invention and make crystallization rate when injection-molded finished in injection moulding, heat treatment step after injection moulding, its annealing time is can reach best mechanical property and the resistance toheat of product in 1-5 minute, be used for body series compared to other nucleator, need long annealing time just can reach best mechanical property and the resistance toheat of product.
Wherein, the described phosphoric acid salt that contains aromatic group can be selected from 4,6-di-tert-butyl-phenyl sodium phosphate, hydroxide 2, one or more compositions in 2-methylene-bis (4,6-di-tert-butyl-phenyl) sodium phosphate salt, phosphenylic acid zinc, phenyl zinc phosphite, phenyl zinc hypophosphite.
Wherein, described talcous particle size range can be 1250 orders ~ 3000 orders, and the present inventor finds by great many of experiments, when talcous particle size range is in 1250 orders ~ 3000 order scopes, the lactic acid composite material resistance toheat of gained is better, and mechanical property is also better.
Wherein, described fiber can be selected from one or more compositions in glass fibre, paper fiber, xylon, bamboo fibers, flax fiber, sisal fibers, kenaf.
Wherein, described coupling agent be in higher fatty acid, titanate coupling agent, aluminate coupling agent, silane coupling agent, epoxy resin one or more compositions.
Wherein, described lubricant is one or more compositions in the polymer complex ester, ethylene bis stearamide, polyethylene wax of stearic acid, epoxy soybean oil, hard esteramides, amine hydroxybenzene, erucicamide, Zinic stearas, calcium stearate, aluminum stearate, metallic soap.
A kind of preparation method of lactic acid composite material goods as above,
Step 1) blending extrusion: in proportion poly(lactic acid), oligomeric protein multipolymer, Biodegradable polyester are mixed in mixer, obtain Preblend, dry described Preblend; To contain in proportion phosphoric acid salt, talcum powder, fiber, coupling agent, lubricant and the described Preblend of aromatic group in high-speed mixer and mixing, resulting compound; Compound is fed carry out fusion plastification in twin screw extruder, extrude, pelletizing, obtain the lactic acid composite material particle;
Step 2) injection moulding: the lactic acid composite material particle that step 1) is obtained is at the injection moulding machine compacted under;
Step 3) thermal treatment: with step 2) products formed that obtains obtains the lactic acid composite material goods 100-120 ℃ of annealing.
Wherein, step 2) injection moulding specifically: be 150-250 ℃ with the particle after above-mentioned extruding pelletization in temperature, pressure is injection moulding in injection moulding machine under the condition of 60-160Mpa;
Step 3) thermal treatment: with step 2) products formed that obtains is that under the condition of 100-120 ℃, annealing obtained the lactic acid composite material goods in 1-5 minute in temperature.
A kind of application of lactic acid composite material as mentioned above is characterized in that:
Described lactic acid composite material is applied to the XX field.
Compare prior art, lactic acid composite material of the present invention, added oligomeric protein multipolymer of the present invention in its raw material, improved the thermotolerance of lactic acid composite material, the consistency of matrix material and its thermotolerance of preparation-obtained goods and resulting materials is good, and mechanical property is good.
Embodiment
Below in conjunction with some embodiments, lactic acid composite material of the present invention, preparation method and application thereof are described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
The material that embodiment of the present invention is used and source thereof:
Poly(lactic acid): PLA, Nature work4032D, Cargill Dow company, MFR (melt flow rate (MFR)) 3g/10min (190 ° of C/2.16kg);
The present embodiment oligomeric protein multipolymer used is provided by Mitsui chemical company:
Oligomeric protein copolymer-1: amino-succinic acid-rac-Lactide-1, weight-average molecular weight 9000, rac-Lactide molar content 85%;
Oligomeric protein multipolymer-2: α-aminopropionic acid-lactide copolymer, weight-average molecular weight 10000, rac-Lactide molar content 85%;
Oligomeric protein multipolymer-3: β-alanine-lactide copolymer, weight-average molecular weight 6000, rac-Lactide molar content 85%;
Oligomeric protein multipolymer-4: beta-aminobutyric acid-lactide copolymer, weight-average molecular weight 8000, rac-Lactide molar content 85%;
Oligomeric protein multipolymer-5: γ--aminobutyric acid-lactide copolymer, weight-average molecular weight 9500, rac-Lactide molar content 85%;
Amino-succinic acid-rac-Lactide-2: weight-average molecular weight 9000, rac-Lactide molar content 95% amino-succinic acid-rac-Lactide-3: weight-average molecular weight 9000, rac-Lactide molar content 90%;
Amino-succinic acid-rac-Lactide-4: weight-average molecular weight 9000, rac-Lactide molar content 80%;
Amino-succinic acid-rac-Lactide-5: weight-average molecular weight 9000, rac-Lactide molar content 70%;
Poly butylene succinate: Mw=14-15 ten thousand, Japan clear and polymer company;
3-hydroxybutyrate ester-4-hydroxyl valerate: Mirel P4001, U.S. metlibox company;
The multipolymer of 3-hydroxybutyrate and 3-hydroxypentanoic acid: Mw=10-20 ten thousand, Ningbo Tianan Biological Material Co., Ltd.
Poly butyric ester: Mw=10-20 ten thousand, Ningbo Tianan Biological Material Co., Ltd.
Succinic acid/mutual-phenenyl two acid bromide two alcohol ester: Mw=10-20 ten thousand, Japan clear and polymer company.
Detection method or standard that embodiment of the present invention is used are:
Tensile strength is pressed the ISO527 standard testing;
Elongation at break by standard ISO 527-2/5A/500 test, is to test under the condition of 23 ℃ at probe temperature;
The socle girder notched Izod impact strength is pressed the ISO180 standard testing, and the type of socle girder breach is the category-A breach;
Vicat softening temperature: by the method test of standard ISO 306-2005 regulation.
Embodiment 1
Get 40 parts of poly(lactic acid), 5 parts of amino-succinic acid-lactide copolymers, 15 parts of poly butylene succinates, 1 part of phenyl zinc phosphite, 20 parts of talcum powder, 20 parts of xylons, silane coupling agent γ-0.2 part of (2,3-epoxy the third oxygen) propyl trimethoxy silicane, 0.3 part, lubricant stearic acid aluminium.Put into baking oven after polylactic acid PLA is mixed according to proportioning with poly butylene succinate, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h, screw speed: 300rpm, vacuum pressure: 0.4 normal atmosphere.
Be 180 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 100MPa, is annealing 2 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 1.
Embodiment 2
Get 30 parts of poly(lactic acid), 20 parts of α-aminopropionic acid-lactide copolymers, 3-hydroxybutyrate ester-20 parts of 4-hydroxyl pentanoate copolymers, 1 part of 4,6-di-tert-butyl-phenyl sodium phosphate, 10 parts of talcum powder, 20 parts, glass fibre, 0.2 part of titanate coupling agent, 0.3 part of lubricant stearic acid calcium.With polylactic acid PLA with put into baking oven after 3-hydroxybutyrate ester-4-hydroxyl pentanoate copolymer mixes according to proportioning, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere.Be 190 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 110MPa, is annealing 3 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 1.
Embodiment 3
Get 50 parts of poly(lactic acid), 10 parts of β-alanine-lactide copolymers, 5 parts of the copolymer 1s of 3-hydroxybutyrate and 3-hydroxypentanoic acid, 1 part, phosphenylic acid zinc, 15 parts of talcum powder, 10 parts of paper fibers, 0.3 part of titanate coupling agent, 0.2 part of the hard esteramides of lubricant.With polylactic acid PLA with put into baking oven after 3-hydroxybutyrate ester-4-hydroxyl pentanoate copolymer mixes according to proportioning, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere.Be 180 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 120MPa, is annealing 2 minutes under the condition of 110 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 1.
Embodiment 4
Get 45 parts of poly(lactic acid), 10 parts of beta-aminobutyric acid-lactide copolymers, succinic acid/5 parts of mutual-phenenyl two acid bromide two alcohol ester's copolymer 1s, hydroxide 2,2 parts of 2-methylene-bis (4,6-di-tert-butyl-phenyl) sodium phosphate salts, 20 parts of talcum powder, 10 parts of kenaves, 0.5 part of higher fatty acid, 0.5 part of lubricant erucicamide.With polylactic acid PLA with put into baking oven after 3-hydroxybutyrate ester-4-hydroxyl pentanoate copolymer mixes according to proportioning, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere; Be 200 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 100MPa, is annealing 2 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 1.
Embodiment 5
Get 60 parts of poly(lactic acid), 5 parts of γ-aminobutyric acid-lactide copolymers, 5 parts of poly butyric esters, 5 parts, phosphenylic acid zinc, 20 parts of talcum powder, 10 parts of flax fiber fibers, 1 part of aluminate coupling agent, 1 part of lubricant ethylene bis stearamide.Put into baking oven after polylactic acid PLA is mixed according to proportioning with poly butyric ester, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere; Be 190 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 100MPa, is annealing 5 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 1.
Embodiment 6
Get 45 parts of poly(lactic acid), 5 parts of amino-succinic acid-lactide copolymers, 20 parts of poly butylene succinates, hydroxide 2,1 part of 2-methylene-bis (4,6-di-tert-butyl-phenyl) sodium phosphate salt, 20 parts of talcum powder, 10 parts of flax fiber fibers, 0.3 part of aluminate coupling agent, 0.3 part, lubricant stearic acid zinc.Put into baking oven after polylactic acid PLA is mixed according to proportioning with poly butylene succinate, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere.Be 180 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 150MPa, is annealing 3 minutes under the condition of 110 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 1.
Embodiment 7
Get 40 parts of poly(lactic acid), 5 parts of amino-succinic acid-lactide copolymers, 15 parts of poly butylene succinates, 1 part of phthalocyanine ketone, 20 parts of talcum powder, 20 parts of xylons, silane coupling agent γ-0.2 part of (2,3-epoxy the third oxygen) propyl trimethoxy silicane, 0.3 part, lubricant stearic acid aluminium.Put into baking oven after polylactic acid PLA is mixed according to proportioning with poly butylene succinate, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h, screw speed: 300rpm, vacuum pressure: 0.4 normal atmosphere.
Be 180 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 100MPa, is annealing 30 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 1.
Embodiment 8
Get 40 parts of poly(lactic acid), 5 parts of amino-succinic acid-lactide copolymers, 3-hydroxybutyrate ester-15 parts of 4-hydroxyl pentanoate copolymers, 1 part of octane dicarboxylic acid dibenzoyl hydrazine, 20 parts of talcum powder, 20 parts, glass fibre, 0.2 part of titanate coupling agent, 0.3 part of lubricant stearic acid calcium.With polylactic acid PLA with put into baking oven after 3-hydroxybutyrate ester-4-hydroxyl pentanoate copolymer mixes according to proportioning, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere.
Be 190 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 110MPa, is annealing 30 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 1.
Table 1
Comparative Examples 1
Get 45 parts of poly(lactic acid), 15 parts of poly butylene succinates, 1 part of phenyl zinc phosphite, 20 parts of talcum powder, 20 parts of xylons, silane coupling agent γ-0.2 part of (2,3-epoxy the third oxygen) propyl trimethoxy silicane, 0.3 part, lubricant stearic acid aluminium.Put into baking oven after polylactic acid PLA is mixed according to proportioning with poly butylene succinate, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h, screw speed: 300rpm, vacuum pressure: 0.4 normal atmosphere.
Be 180 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 100MPa, is annealing 2 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 2.
Comparative Examples 2
Get 50 parts of poly(lactic acid), 3-hydroxybutyrate ester-20 parts of 4-hydroxyl pentanoate copolymers, 1 part of 4,6-di-tert-butyl-phenyl sodium phosphate, 10 parts of talcum powder, 20 parts, glass fibre, 0.2 part of titanate coupling agent, 0.3 part of lubricant stearic acid calcium.With polylactic acid PLA with put into baking oven after 3-hydroxybutyrate ester-4-hydroxyl pentanoate copolymer mixes according to proportioning, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere.Be 190 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 110MPa, is annealing 3 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 2.
Comparative Examples 3
Get 60 parts of poly(lactic acid), 5 parts of the copolymer 1s of 3-hydroxybutyrate and 3-hydroxypentanoic acid, 1 part, phosphenylic acid zinc, 15 parts of talcum powder, 10 parts of paper fibers, 0.3 part of titanate coupling agent, 0.2 part of the hard esteramides of lubricant.With polylactic acid PLA with put into baking oven after 3-hydroxybutyrate ester-4-hydroxyl pentanoate copolymer mixes according to proportioning, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere.Be 180 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 120MPa, is annealing 2 minutes under the condition of 110 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 2.
Comparative Examples 4
Get 55 parts of poly(lactic acid), succinic acid/5 parts of mutual-phenenyl two acid bromide two alcohol ester's copolymer 1s, hydroxide 2,2 parts of 2-methylene-bis (4,6-di-tert-butyl-phenyl) sodium phosphate salts, 20 parts of talcum powder, 10 parts of kenaves, 0.5 part of higher fatty acid, 0.5 part of lubricant erucicamide.With polylactic acid PLA with put into baking oven after 3-hydroxybutyrate ester-4-hydroxyl pentanoate copolymer mixes according to proportioning, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere; Be 200 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 100MPa, is annealing 2 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 2.
Comparative Examples 5
Get 65 parts of poly(lactic acid), 5 parts of poly butyric esters, 5 parts, phosphenylic acid zinc, 20 parts of talcum powder, 10 parts of flax fiber fibers, 1 part of aluminate coupling agent, 1 part of lubricant ethylene bis stearamide.Put into baking oven after polylactic acid PLA is mixed according to proportioning with poly butyric ester, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere; Be 190 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 100MPa, is annealing 5 minutes under the condition of 100 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 2.
Comparative Examples 6
Get 50 parts of poly(lactic acid), 20 parts of poly butylene succinates, hydroxide 2,1 part of 2-methylene-bis (4,6-di-tert-butyl-phenyl) sodium phosphate salt, 20 parts of talcum powder, 10 parts of flax fiber fibers, 0.3 part of aluminate coupling agent, 0.3 part, lubricant stearic acid zinc.Put into baking oven after polylactic acid PLA is mixed according to proportioning with poly butylene succinate, carried out removal moisture drying 8 hours under 50-80 ℃ of condition; Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning; Use weighing balance accurate measurement feeding forcing machine.The forcing machine length-to-diameter ratio is 60:1; Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder; Melting temperature is as follows: one section 80-90 ℃; Two sections 80-90 ℃; Three sections 90-100 ℃; Four sections 90-100 ℃; Five sections 100-110 ℃; Six sections 140-150 ℃; Seven sections 180-190 ℃; Eight sections 200-210 ℃; Nine sections 200-210 ℃; Head 180-190 ℃; Rate of feeding: 100kg/h; Screw speed: 300rpm; Vacuum pressure: 0.4 normal atmosphere.Be 180 ℃ in temperature after granulation, pressure is injection moulding in injection moulding machine under the condition of 150MPa, is annealing 3 minutes under the condition of 110 ℃ in temperature with the sheet material of injection moulding.Its mechanical property and resistance toheat see Table 2.
Table 2
Contrast one by one by embodiment 1-6 and Comparative Examples 1-6, after having added the oligomeric blend of amino acid-rac-Lactide in lactic acid composite material of the present invention, its mechanical property and resistance toheat all are improved.
Embodiment 9-12
With reference to preparation method and the formula of embodiment 1, according to shown in table 3, replace amino-succinic acid-lactide copolymer with different amino acid-lactide copolymer and make raw material, the preparation lactic acid composite material, its mechanical property and anti-corrosion performance are listed in table 3.
Table 3
Compared by embodiment 1 and embodiment 9-12, under same formula, when amino acid-when the rac-Lactide oligopolymer was the multipolymer of amino-succinic acid and rac-Lactide, its mechanical property and resistance toheat were better.
Embodiment 13
With reference to preparation method and the formula of embodiment 1, according to shown in table 4, the preparation lactic acid composite material, wherein the molar weight of the rac-Lactide in raw material amino-succinic acid-lactide copolymer is 95%, its mechanical property and anti-corrosion performance are listed in table 4.
Embodiment 14
With reference to preparation method and the formula of embodiment 1, according to shown in table 4, the preparation lactic acid composite material, wherein the molar weight of the rac-Lactide in raw material amino-succinic acid-lactide copolymer is 90%, its mechanical property and anti-corrosion performance are listed in table 4.
Embodiment 15
With reference to preparation method and the formula of embodiment 1, according to shown in table 4, the preparation lactic acid composite material, wherein the molar weight of the rac-Lactide in raw material amino-succinic acid-lactide copolymer is 80%, its mechanical property and anti-corrosion performance are listed in table 4.
Embodiment 16
With reference to preparation method and the formula of embodiment 1, according to shown in table 4, the preparation lactic acid composite material, wherein the molar weight of the rac-Lactide in raw material amino-succinic acid-lactide copolymer is 70%, its mechanical property and anti-corrosion performance are listed in table 4.
Table 4
| ? | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 |
| Poly(lactic acid) | 40 | 40 | 40 | 40 |
| Amino-succinic acid-lactide copolymer | 5 | 5 | 5 | 5 |
| Poly butylene succinate | 15 | 15 | 15 | 15 |
| The phenyl zinc phosphite | 1 | 1 | 1 | 1 |
| Talcum powder | 20 | 20 | 20 | 20 |
| Xylon | 20 | 20 | 20 | 20 |
| Coupling agent | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant | 0.3 | 0.3 | 0.3 | 0.3 |
| Tensile strength/MPa | 45 | 38 | 42 | 35 |
| Elongation at break/% | 20 | 18 | 16 | 15 |
| Notched Izod impact strength (KJ/m 2） | 15 | 10 | 12 | 8 |
| Vicat softening temperature/℃ | 140 | 148 | 138 | 120 |
Can find out from embodiment 13-16, when the molar content of rac-Lactide in amino-succinic acid-lactide copolymer was 80-95%, mechanical property and the resistance toheat of the lactic acid composite material of preparation gained were better.
The above is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in scope of patent protection of the present invention.
Claims (10)
1. lactic acid composite material, its main component is for comprising by weight:
Poly(lactic acid) 30-60 part;
Oligomeric protein multipolymer 5-10 part;
Biodegradable polyester 5-20 part;
Nucleator 0.1-5 part;
Talcum powder 5-20 part;
Fiber 5-20 part;
Coupling agent 0.1-1 part;
Lubricant 0.1-1 part;
Wherein, described oligomeric protein multipolymer is the polymkeric substance of amino acid and rac-Lactide, and the weight-average molecular weight of described oligomeric protein multipolymer is less than or equal to 10,000.
2. lactic acid composite material, by following composition for forming by weight:
Poly(lactic acid) 30-60 part;
Oligomeric protein multipolymer 5-10 part;
Biodegradable polyester 5-20 part;
Nucleator 0.1-5 part;
Talcum powder 5-20 part;
Fiber 5-20 part;
Coupling agent 0.1-1 part;
Lubricant 0.1-1 part;
Wherein, described oligomeric protein multipolymer is the multipolymer of amino acid and rac-Lactide, and the weight-average molecular weight of described oligomeric protein multipolymer is less than or equal to 10,000.
3. lactic acid composite material as claimed in claim 1 or 2 is characterized in that:
Described amino acid is selected from one or more in amino-succinic acid, α-aminopropionic acid, β-alanine, butyrine, beta-aminobutyric acid, γ-aminobutyric acid.
4. lactic acid composite material as claimed in claim 1 or 2 is characterized in that:
The amino acid of described preparation oligomeric protein multipolymer is (5-20) with the ratio of the molar weight of rac-Lactide: (80-95).
5. lactic acid composite material as claimed in claim 1 or 2 is characterized in that:
Described Biodegradable polyester is selected from the multipolymer of multipolymer, hydroxybutyric acid and hydroxycaproic acid of poly butylene succinate, poly--3-hydroxybutyrate ester, 3-hydroxybutyrate and 3-hydroxypentanoic acid, one or more mixtures of succinic acid/mutual-phenenyl two acid bromide two alcohol ester.
6. lactic acid composite material as claimed in claim 1 or 2 is characterized in that:
Described nucleator is the phosphoric acid salt that contains aromatic group.
7. lactic acid composite material as claimed in claim 1 or 2 is characterized in that:
Described talcous particle size range is 1250 orders ~ 3000 orders.
8. lactic acid composite material as claimed in claim 1 or 2 is characterized in that:
Described fiber is selected from one or more compositions in glass fibre, paper fiber, xylon, bamboo fibers, flax fiber, sisal fibers, kenaf.
9. preparation method as lactic acid composite material goods as described in claim 1-8 any one, its feature
Be:
Step 1) blending extrusion: in proportion poly(lactic acid), oligomeric protein multipolymer, Biodegradable polyester are mixed in mixer, obtain Preblend, dry described Preblend; To contain in proportion phosphoric acid salt, talcum powder, fiber, coupling agent, lubricant and the described Preblend of aromatic group in high-speed mixer and mixing, resulting compound; Compound is fed carry out fusion plastification in twin screw extruder, extrude, pelletizing, obtain the lactic acid composite material particle;
Step 2) injection moulding: the lactic acid composite material particle that step 1) is obtained is at the injection moulding machine compacted under;
Step 3) thermal treatment: with step 2) products formed that obtains obtains the lactic acid composite material goods 100-120 ℃ of annealing.
10. application as lactic acid composite material as described in claim 1-8 any one is characterized in that:
Described lactic acid composite material is applied to the fields such as injection molding product, extrusion board, sheet material and corresponding Blister product.
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| CN105153659A (en) * | 2015-10-16 | 2015-12-16 | 深圳市绿意包装有限公司 | Heat resistant polylactic acid composite material and preparation method thereof |
| CN105566874A (en) * | 2016-02-06 | 2016-05-11 | 浙江双枪竹木有限公司 | Polylactic acid and bamboo powder compounded modified material |
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| CN108752887A (en) * | 2018-06-20 | 2018-11-06 | 瞿向东 | A kind of environment-friendly type degradable composite material for disposable vaginal dilator |
| CN109735074A (en) * | 2019-01-11 | 2019-05-10 | 中纺协检验（泉州）技术服务有限公司 | A kind of environment-friendly degradable fiber shoes materials and preparation method thereof |
| CN109735074B (en) * | 2019-01-11 | 2020-11-17 | 中纺协检验（泉州）技术服务有限公司 | Environment-friendly degradable fiber shoe material and preparation method thereof |
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