CN106565992B - A kind of starch load polylactic acid crystal nucleating agent and preparation method thereof - Google Patents
A kind of starch load polylactic acid crystal nucleating agent and preparation method thereof Download PDFInfo
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- CN106565992B CN106565992B CN201710000859.6A CN201710000859A CN106565992B CN 106565992 B CN106565992 B CN 106565992B CN 201710000859 A CN201710000859 A CN 201710000859A CN 106565992 B CN106565992 B CN 106565992B
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- starch
- polylactic acid
- nucleating agent
- phenyl
- phosphonic acid
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 81
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 79
- 229920002472 Starch Polymers 0.000 title claims abstract description 75
- 239000008107 starch Substances 0.000 title claims abstract description 75
- 235000019698 starch Nutrition 0.000 title claims abstract description 75
- 239000003484 crystal nucleating agent Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002667 nucleating agent Substances 0.000 claims abstract description 28
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000011010 flushing procedure Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims abstract description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 240000003183 Manihot esculenta Species 0.000 claims description 5
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 5
- FBJSQCNXGBALGR-UHFFFAOYSA-N barium;phenylphosphonic acid Chemical compound [Ba].OP(O)(=O)C1=CC=CC=C1 FBJSQCNXGBALGR-UHFFFAOYSA-N 0.000 claims description 5
- WQJURGLUMGXTAR-UHFFFAOYSA-N phenylphosphonic acid;zinc Chemical compound [Zn].OP(O)(=O)C1=CC=CC=C1 WQJURGLUMGXTAR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- KPIFANRKBGFSOZ-UHFFFAOYSA-N calcium;phenylphosphonic acid Chemical compound [Ca].OP(O)(=O)C1=CC=CC=C1 KPIFANRKBGFSOZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 27
- 238000012545 processing Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 4
- 239000008120 corn starch Substances 0.000 description 4
- 229940099112 cornstarch Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000479 mixture part Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- 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
- C08K2201/018—Additives for biodegradable polymeric composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
A kind of starch load polylactic acid crystal nucleating agent and preparation method thereof, raw material composition include starch and Phenylphosphine hydrochlorate, and weight is 9 99:1.Preparation method is：A, starch is dried, B, aqueous chloride solution is poured into after drying in starch, starch mixture is made in stirring, C, 100 parts by weight of starch mixture are added in 1000 parts of the phenyl-phosphonic acid aqueous solution that mass concentration is 20%, it is sufficiently stirred reaction 25 35 minutes, then separating and filtering, is used in combination distilled water flushing 46 times, cleared unreacted phenyl-phosphonic acid, 95 105oAt a temperature of C, dry 3.5 4.5h, as starch load nucleating agent in polylactic acid production.Invention effect：Due to the nucleating agent high degree of dispersion of generation, the nucleating point of mass efficient is formed on surface, realizes that nucleating agent dosage is few, reduces cost, improve the purpose of nucleation efficiencies.
Description
Technical field
The present invention relates to a kind of crystallization nucleating agent of polylactic acid more particularly to a kind of carbon starch load polylactic acid crystal nucleation
Agent and preparation method thereof belongs to biodegradated polymer materal technical field.
Background
In numerous developed biodegradated polymer materals, polylactic acid（PLA）It is known as most potential product
One of kind.The thermoplastic aliphatic polyester of its fully biodegradable is a kind of nontoxic, nonirritant, has good biological phase
Capacitive, it is biodegradable absorb, mechanical strength is high, the biodegradated polymer materal of plasticity machine-shaping.With other chemistry
Synthesising biological degraded macromolecular is compared, and the maximum feature of polylactic acid is that it comes from reproducible plant resources, has been broken away to stone
The raw material of the dependence of oily resource, synthesizing polylactic acid can be obtained from crops such as corn, stalks.Currently, polylactic acid application is restricted
Principal element with development includes：Crystalline rate is slow, crystallinity is low, heat distortion temperature is relatively low, brittleness is big etc..Due to material crystalline
Rate is slow, polylactic acid article obtained by actual production（Such as injection moulding）Generally in amorphous state, when its glass transition temperature with
Above in use, mechanical strength will be remarkably decreased with rigidity, cause the product transparency bad and fragility fracture, largely
On limited to the processing and application of polylactic acid.Seem for this purpose, exploitation can meet the special nucleating agent that polylactic acid crystal modification needs
Very necessary and urgent, this is also to study the basic original being concerned in relation to polylactic acid crystal behavior and related nucleating agent at present
Cause.
Nucleus of the nucleating agent as crystalline polymer plays while growth, the refinement crystalline size of promotion crystal
The effect for the crystallization rate for improving polymer.At present the crystallization nucleating agent of polylactic acid mainly include inorganic nucleator and it is organic at
Two class of core agent, wherein inorganic nucleator have talcum powder, montmorillonite, calcium lactate etc., the poor compatibility of this kind of nucleating agent and polylactic acid,
Easily reunite and disperse in the polymer uneven, crystalline rate is low, and additive amount mostly can also influence the other performance of material.It is organic at
Core agent such as low molecular weight aliphatic amine, the fatty acid metal salts containing Long carbon chain and the phosphonic acids containing phenyl ring, phosphorous acid etc.
Metal salt.
Chinese patent CN105733211A discloses a kind of composition and preparation method thereof containing starch nano particle, tool
Have the advantages that tensile strength is high, impact flexibility is good, elongation at break is big, is suitble to prepare the daily high score high to mechanical property requirements
Sub- material articles for use and device.World patent WO2006055504A2 discloses chemical modification thermoplastic starch and was squeezed out to polylactic acid
Influence in journey in terms of crystallization kinetics obtains preferable processing performance.But starch and the intermolecular forces of polylactic acid are weak, cause
Starch difficulties in dispersion blending effect in polylactic acid is not very ideal, and interface linking is poor, it is necessary to by modified or other are total
Mixed means are come the compatibility that both increases, and compared with conventional talc powder nucleating agent, crystallization facilitating effect still has certain gap.
Invention content
The purpose of the present invention is being directed to starch nucleating agent the deficiencies in the prior art such as effect difference and bad dispersibility are blended, provide
A kind of starch load polylactic acid crystal nucleating agent and preparation method thereof.The nucleating agent can be improved starch in polylactic acid dispersibility and
Nucleation efficiencies are high, and polylactic acid crystal speed, heat resistance can be improved, and improve molding processibility performance, and starch loads polylactic acid nucleation
Agent dosage is few, at low cost and preparation method is simple.
A kind of starch load polylactic acid crystal nucleating agent, raw material composition includes starch and Phenylphosphine hydrochlorate, parts by weight
Proportioning is 9-99:1.
The starch is one kind in cornstarch and tapioca.
The phosphenylic acid salt is one kind in phenyl-phosphonic acid calcium, phenyl-phosphonic acid zinc, phenyl-phosphonic acid barium.
Starch load polylactic acid crystal nucleating agent preparation method be：
A, starch is dried:Starch is used preposition in 95-105oAt a temperature of C, dry 3.5-4.5h,
B, starch mixture processed:Chloride is configured to the aqueous solution of 10%-30% mass concentrations, then according to starch weight
The 0.56%-7.1% of ratio, by aqueous chloride solution pour into it is dry after in starch, be sufficiently stirred 0.8-1.2h at room temperature, starch be made
Mixture,
C, 100 parts by weight of starch mixture are added in 1000 parts of the phenyl-phosphonic acid aqueous solution that mass concentration is 20%, fully
It is stirred to react 25-35 minutes, then separating and filtering, is used in combination distilled water flushing 4-6 times, cleared unreacted phenyl-phosphonic acid, 95-
105 oAt a temperature of C, dry 3.5-4.5h, as starch load nucleating agent in polylactic acid production.
It is using the method that starch load nucleating agent in polylactic acid production processes polylactic acid crystal sample：It is 10- by weight average molecular weight
Starch load polylactic acid crystal nucleating agent 1-10 parts by weight prepared by 400000 100 parts by weight of polylactic acid and the present invention, are added to
It in mixer, is mixed 5-8 minutes under conditions of 175-185 DEG C, 45-55 revs/min, room temperature cools down after mixing, as poly- breast
Acid crystal sample.
Used chloride is one kind in calcium chloride, zinc chloride, barium chloride.
Invention effect：
1. the load polylactic acid crystal nucleating agent of the present invention is using starch as carrier, using the method that substep mixes by phenyl
Phosphonic acids is dispersed in the surface of starch, forms effective polylactic acid crystal nucleating agent.Due to the nucleating agent high degree of dispersion of generation, in table
Face forms the nucleating point of mass efficient, realizes that nucleating agent dosage is few, reduces cost, improve the purpose of nucleation efficiencies.
2. the nucleating agent of the present invention is using starch as main carriers, starch can be biodegradable completely, and as poly-
Lactic acid nucleating agent improves the processing mechanical property to polymer.The nucleating agent is by chloride and phenyl-phosphonic acid reactive deposition in shallow lake
Powder surface, processing cost are low and easily operated.
Specific implementation mode
Comparative examples
Polylactic acid（Weight average molecular weight 400,000）It is added in mixer, 5 points is mixed under conditions of 180 DEG C, 50 revs/min
Clock, mixed sample is cooling directly under air at room temperature state, obtains polylactic acid sample.
The polylactic acid sample obtained cuts into fritter and carries out DSC measurement as sample to be tested：Polylactic acid crystal sample
Sample to be tested is raised to 190 DEG C from room temperature under nitrogen protection, with 50 DEG C/min, stops 2min and eliminates thermal history, then with 10 DEG C/
Min is cooled to 0 DEG C.It is uncrystallizable in this test condition to obtain polylactic acid, crystallinity 0.
Embodiment 1
Cornstarch uses preposition in 100oUnder C, dry 4h.
Barium chloride is configured to the aqueous solution of 10% mass concentration, it is then according to the ratio of starch 3.5% that barium chloride is water-soluble
Liquid pour into it is dry after in starch, be sufficiently stirred 1h at room temperature, be made 100 weight of starch mixture after starch mixture
Part is added in 1000 parts of the phenyl-phosphonic acid aqueous solution that the dense amount of quality is 20%, is sufficiently stirred reaction 30min, then separating and filtering, and
With distilled water flushing 5 times, cleared unreacted phenyl-phosphonic acid, 100 DEG C of dry 4h finally obtain content and form sediment for 5% phenyl-phosphonic acid barium
The nucleating agent in polylactic acid production of powder load.
5 parts by weight of starch load polylactic acid crystal nucleating agent prepared by 100 parts by weight of polylactic acid and the present invention, are added to
In mixer, mixed 8 minutes under conditions of 180 DEG C, 50 revs/min, mixed sample is directly under air at room temperature state
It is cooling, obtain polylactic acid crystal sample.
The polylactic acid crystal sample obtained cuts into fritter and carries out DSC measurement as sample to be tested：Polylactic acid crystal sample
The sample to be tested of product is raised to 190 DEG C from room temperature under nitrogen protection, with 50 DEG C/min, stops 2min and eliminates thermal history, then with
10 DEG C/min is cooled to 0 DEG C.It is 110 DEG C to obtain polylactic acid crystal temperature, crystallinity 38%.
Embodiment 2
Cornstarch processing is the same as embodiment 1.
Calcium chloride is configured to the aqueous solution of 30% mass concentration, it is then according to the ratio of starch 5.6% that calcium chloride is water-soluble
Liquid pour into it is dry after in starch, be sufficiently stirred 1h at room temperature, add the mixture to 20% phenyl-phosphonic acid aqueous solution 1000 later
In part, it is sufficiently stirred reaction 30min, then separating and filtering, is used in combination distilled water flushing 5 times, cleared unreacted phenyl-phosphonic acid,
100 DEG C of dry 4h finally obtain the nucleating agent in polylactic acid production that content is the load of 10% phenyl-phosphonic acid calcium starch.
2.5 parts by weight of starch load polylactic acid crystal nucleating agent prepared by 100 parts by weight of polylactic acid and the present invention, are added
Into mixer, mixed 8 minutes under conditions of 180 DEG C, 50 revs/min, mixed sample is directly in air at room temperature state
Lower cooling, obtains polylactic acid crystal sample.
The DSC processing of polylactic acid crystal sample is the same as embodiment 1.It is 115 DEG C to obtain polylactic acid crystal temperature, crystallinity 41%.
Embodiment 3
Cornstarch processing is the same as embodiment 1.
Zinc chloride is configured to the aqueous solution of 20% mass concentration, it is then according to the ratio of starch 4.6% that zinc chloride is water-soluble
Liquid pour into it is dry after in starch, be sufficiently stirred 1h at room temperature, add the mixture to 20% phenyl-phosphonic acid aqueous solution 1000 later
In part, it is sufficiently stirred reaction 30min, then separating and filtering, is used in combination distilled water flushing 5 times, cleared unreacted phenyl-phosphonic acid,
100 DEG C of dry 4h finally obtain the nucleating agent in polylactic acid production that content is the load of 7.5% phenyl-phosphonic acid zinc starch.
8 parts by weight of starch load polylactic acid crystal nucleating agent prepared by 100 parts by weight of polylactic acid and the present invention, are added to
In mixer, mixed 8 minutes under conditions of 180 DEG C, 50 revs/min, mixed sample is directly under air at room temperature state
It is cooling, obtain polylactic acid crystal sample.
The DSC processing of polylactic acid crystal sample is the same as embodiment 1.It is 118 DEG C to obtain polylactic acid crystal temperature, crystallinity 39%.
Embodiment 4
Tapioca processing is the same as embodiment 1.
Zinc chloride is configured to the aqueous solution of 15% mass concentration, it is then according to the ratio of starch 3.1% that zinc chloride is water-soluble
Liquid pour into it is dry after in starch, be sufficiently stirred 1h at room temperature, add the mixture to 20% phenyl-phosphonic acid aqueous solution 1000 later
In part, it is sufficiently stirred reaction 30min, then separating and filtering, is used in combination distilled water flushing 5 times, cleared unreacted phenyl-phosphonic acid,
100 DEG C of dry 4h finally obtain the nucleating agent in polylactic acid production that content is the load of 5% phenyl-phosphonic acid zinc starch.
10 parts by weight of starch load polylactic acid crystal nucleating agent prepared by 100 parts by weight of polylactic acid and the present invention, are added
Into mixer, mixed 8 minutes under conditions of 180 DEG C, 50 revs/min, mixed sample is directly in air at room temperature state
Lower cooling, obtains polylactic acid crystal sample.
The DSC processing of polylactic acid crystal sample is the same as embodiment 1.It is 120 DEG C to obtain polylactic acid crystal temperature, crystallinity 42%.
Embodiment 5
Tapioca processing is the same as embodiment 1.
Barium chloride is configured to the aqueous solution of 25% mass concentration, it is then according to the ratio of starch 1.8% that barium chloride is water-soluble
Liquid pour into it is dry after in starch, be sufficiently stirred 1h at room temperature, add the mixture to 20% phenyl-phosphonic acid aqueous solution 1000 later
In part, it is sufficiently stirred reaction 30min, then separating and filtering, is used in combination distilled water flushing 5 times, cleared unreacted phenyl-phosphonic acid,
100 DEG C of dry 4h finally obtain the nucleating agent in polylactic acid production that content is the load of 2.5% phenyl-phosphonic acid barium starch.
6 parts by weight of starch load polylactic acid crystal nucleating agent prepared by 100 parts by weight of polylactic acid and the present invention, are added to
In mixer, mixed 8 minutes under conditions of 180 DEG C, 50 revs/min, mixed sample is directly under air at room temperature state
It is cooling, obtain polylactic acid crystal sample.
The DSC processing of polylactic acid crystal sample is the same as embodiment 1.It is 112 DEG C to obtain polylactic acid crystal temperature, crystallinity 36%.
Embodiment 6
Tapioca processing is the same as embodiment 1.
Calcium chloride is configured to the aqueous solution of 20% mass concentration, it is then according to the ratio of starch 0.56% that calcium chloride is water-soluble
Liquid pour into it is dry after in starch, be sufficiently stirred 1h at room temperature, add the mixture to 20% phenyl-phosphonic acid aqueous solution 1000 later
In part, it is sufficiently stirred reaction 30min, then separating and filtering, is used in combination distilled water flushing 5 times, cleared unreacted phenyl-phosphonic acid,
100 DEG C of dry 4h finally obtain the nucleating agent in polylactic acid production that content is the load of 1% phenyl-phosphonic acid barium starch.
1 parts by weight of starch load polylactic acid crystal nucleating agent prepared by 100 parts by weight of polylactic acid and the present invention, are added to
In mixer, mixed 8 minutes under conditions of 180 DEG C, 50 revs/min, mixed sample is directly under air at room temperature state
It is cooling, obtain polylactic acid crystal sample.
The DSC processing of polylactic acid crystal sample is the same as embodiment 1.It is 114 DEG C to obtain polylactic acid crystal temperature, crystallinity 37%.
Claims (4)
1. a kind of starch loads polylactic acid crystal nucleating agent, it is characterised in that its raw material composition includes starch and Phenylphosphine hydrochlorate,
Its weight is 9-99:1；
The starch load polylactic acid crystal nucleating agent is prepared in accordance with the following methods：
A, starch is dried:Starch is used into preposition at a temperature of 95-105 DEG C, dry 3.5-4.5h；
B, starch mixture processed:Chloride is configured to the aqueous solution of 10%-30% mass concentrations, then according to starch weight than
0.56%-7.1%, by aqueous chloride solution pour into it is dry after in starch, be sufficiently stirred 0.8-1.2h at room temperature, starch mixing be made
Object；
C, 100 parts by weight of starch mixture are added in 1000 parts of the phenyl-phosphonic acid aqueous solution that mass concentration is 20%, are sufficiently stirred
Reaction 25-35 minutes, then separating and filtering, is used in combination distilled water flushing 4-6 times, cleared unreacted phenyl-phosphonic acid, 95-105 DEG C
At a temperature of, dry 3.5-4.5h obtains starch load nucleating agent in polylactic acid production.
2. starch according to claim 1 loads polylactic acid crystal nucleating agent, it is characterised in that the starch forms sediment for corn
One kind in powder and tapioca.
3. starch according to claim 1 loads polylactic acid crystal nucleating agent, it is characterised in that the phosphenylic acid salt is
One kind in phenyl-phosphonic acid calcium, phenyl-phosphonic acid zinc, phenyl-phosphonic acid barium.
4. starch according to claim 1 loads polylactic acid crystal nucleating agent, it is characterised in that used chloride is
One kind in calcium chloride, zinc chloride, barium chloride.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710000859.6A CN106565992B (en) | 2017-01-03 | 2017-01-03 | A kind of starch load polylactic acid crystal nucleating agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710000859.6A CN106565992B (en) | 2017-01-03 | 2017-01-03 | A kind of starch load polylactic acid crystal nucleating agent and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106565992A CN106565992A (en) | 2017-04-19 |
| CN106565992B true CN106565992B (en) | 2018-08-07 |
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|---|---|---|---|---|
| US7153354B2 (en) * | 2004-11-19 | 2006-12-26 | Board Of Trustees Of Michigan State University | Chemically modified plasticized starch compositions by extrusion processing |
| CN101602884B (en) * | 2009-06-25 | 2012-02-22 | 浙江海正生物材料股份有限公司 | Heat-resistant polylactic acid composite material and preparation method thereof |
| CN102212257A (en) * | 2011-04-11 | 2011-10-12 | 中国科学院长春应用化学研究所 | Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof |
| CN102584567B (en) * | 2011-12-29 | 2014-06-25 | 大连理工大学 | Efficient polylactic acid nucleating agent, and preparation method and application thereof |
| CN104877317B (en) * | 2015-05-29 | 2016-10-26 | 江南大学 | A kind of melted after can the preparation method of the quick full bio-based composite material of Stereocomplex |
| CN105733211B (en) * | 2016-05-17 | 2019-06-21 | 江南大学 | Composition and preparation method thereof containing starch nano particle |
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2017
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Denomination of invention: A starch loaded polylactic acid crystallization nucleating agent and its preparation method Granted publication date: 20180807 Pledgee: Industrial and Commercial Bank of China Limited Jingmen Duodao Branch Pledgor: HUBEI GUANGHE BIO-TECH Co.,Ltd. Registration number: Y2024980002786 |