CN106519610A - Method for rapid crystallization of polymer at high temperature - Google Patents
Method for rapid crystallization of polymer at high temperature Download PDFInfo
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- CN106519610A CN106519610A CN201610952275.4A CN201610952275A CN106519610A CN 106519610 A CN106519610 A CN 106519610A CN 201610952275 A CN201610952275 A CN 201610952275A CN 106519610 A CN106519610 A CN 106519610A
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- 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
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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- 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
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- 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
- C08L2205/24—Crystallisation aids
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Abstract
The invention discloses a method for rapid crystallization of a polymer at high temperature. The method includes the steps of (1) subjecting a polymer and an organic nucleating agent to melt blending according to a weight part at a first temperature to obtain a uniformly dispersed composition; and (2) shearing the composition at a second temperature to promote rapid crystallization of the polymer. At the second temperature, the semi-crystallization time t1/2 of the polymer material is shortened to less than 25min, thus endowing the material with excellent physical and mechanical properties and heat resistance, etc.
Description
Technical field
The present invention relates to technical field of polymer materials, the side of more particularly to a kind of polymer rapid crystallization at high temperature
Method.
Background technology
Polyester material is due to outstanding advantages such as wide, the easy to process, light weights of raw material sources, each in current national economy
There is quite varied application in field.But crystalline polyester material molecule chain compliance difference causes, and its crystalline rate is slow, crystallization
Low problem is spent, this causes, and the molding cycle length of polyester material, heat resisting temperature is low, the strength of materials is not high.These problems are constrained
The development and application of polyester, especially as the application of engineering material.Therefore, it is polyester to improve the crystalline rate of polyester and degree of crystallinity
Problem most in the urgent need to address in industry development.
At present, it is to improve crystallizing polyester performance as nucleator to add inorganic compound or organic micromolecule compound etc.
A kind of main path.The patent of Publication No. CN103467947B discloses one kind and uses talcum powder to improve poly- as nucleator
The method of lactic acid crystal property so that the crystallization enthalpy of PLA is improved to 46.8J/g；Publication No. CN 103804864A's
Patent discloses a kind of method for promoting PLA and its material modified crystal property using rigid multiamide class nucleator, will be many
Amide-type nucleator can be such that material flexible chain at 110 DEG C is reduced to 1.6min by 26.2min in adding PLA.
Although prior art can improve the crystalline rate and degree of crystallinity of polyester to a certain extent, it is confined to compared with low temperature
Degree, promotes crystallizing polyester to be still a technical barrier urgently to be resolved hurrily at high temperature, this be primarily due to polymer in high temperature and
Under low temperature, cerium sulphate crystal mechanism is different.
A kind of patent CN105199348A " preparation side of high-intensity high-tenacity heat-proof polylactic acid basal lamina material of the applicant
Although the method carries out hot-stretch more than vitrification point, process PLA basal lamina material forms substantial amounts of shishi- to method "
Kebab structures simultaneously obtain high-intensity high-tenacity heat-proof polylactic acid, but the method must be pressed into after melting to PLA
Diaphragm is simultaneously quickly cooled to below glass transition temperature, and crystallization does not occur in need to ensureing cooling procedure, is then set with other
Polylactic acid crystal can just be made for diaphragm is risen to draft temperature again.Not only complex process is difficult to operate continuously, and its induction is poly-
The crystallization of lactic acid is cold crystallization process, and the temperature of crystallization is relatively low.It can be seen that, the crystalline rate after PLA melting in cooling procedure is still
Need to improve, PLA base product preparation technology still needs to simplify.
Therefore, the application widened by polyester, is badly in need of a kind of simple and effectively method improves the crystallization of polyester simultaneously
Speed and degree of crystallinity so that polyester rapid crystallization.
The content of the invention
In view of this, a kind of problem that the present invention is present for prior art, there is provided method of polyester rapid crystallization.This
Bright process is simple, it is widely applicable, it is adapted to industrialized production, the crystal property of polyester can be obviously improved.
The present invention proposes that a kind of method of polymer rapid crystallization under high temperature is comprised the following steps：
(1) by polymer, melt blending obtains finely dispersed at the first temperature by weight ratio with organic nucleating agent
Composition；
(2) above-mentioned composition is warming up to nucleator to be dissolved completely in polymer, forms homogeneous mixture；
(3) apply shearing to the homogeneous mixture that above-mentioned (2) obtain at the second temperature, you can promote polymer quickly to tie
It is brilliant.
The present invention proposes that a kind of method of polymer rapid crystallization can also be comprised the following steps：
(1) by polymer, melt blending obtains finely dispersed at the first temperature by weight ratio with organic nucleating agent
Composition；
(2) apply shearing to above-mentioned composition at the second temperature, you can promote polymer rapid crystallization.
Alternatively, the melt blending can be set by the processing of the general-purpose plastics such as rotor banbury, screw extruder, inflation film manufacturing machine
It is standby to realize.
Polymer can be realized dissolving each other with the organic nucleating agent at a certain temperature, i.e., organic nucleating agent is with molecular level
It is scattered in polymeric matrix.
It is preferred that the first temperature described in said method is 1～50 DEG C of more than melting point polymer, preferably melting point polymer
5～30 DEG C of the above, second temperature are 1～80 DEG C of below melting point polymer, 20～50 DEG C preferably below melting point polymer.
First temperature is then difficult to melting mixing less than the temperature range, is then easily caused polymerization higher than the temperature range
Thing is degraded and weakens polymer machinery performance；Higher than the temperature range, then molecular relaxation accounts for leading role and notable to second temperature
Weaken effect of the shearing to polymer crystallization, then molecular chain movement is limited and cause crystallization to promote not show less than the temperature range
Write.
It is preferred that the speed of the shearing is 0.2～20rad/s, shear time is 0.1～300s.
Alternatively, the polymer is PLA, polyhydroxyalkanoate, poly butylene succinate, adipic acid-to benzene
Two ester copolymer of dioctyl phthalate fourth, polyethylene terephthalate, polybutylene terephthalate (PBT), polypropylene and propylene copolymerization
At least one in thing.
Alternatively, in the composition, the content of polymer is 90～99.9 weight portions, and the content of organic nucleating agent is 0.1
～2 weight portions.Wherein described organic nucleating agent is at least one in the amides compound containing multiple-CONH- functional groups
Or at least amides compound containing 1-HNCOCONH- functional group, the functional group on the one hand can be with above-mentioned polymer point
Subchain forms hydrogen bond, promotes its compatibility, reduces solution temperature of the organic nucleating agent in polymeric matrix, has on the other hand made
Between machine nucleation agent molecule can by hydrogen bond action be self-assembled into for threadiness or needle-like crystallite, further induce above-mentioned polymerization
Thing is in its surface crystallization.
Above-mentioned organic nucleating agent is specifically included but is not limited to：N, N ' -1,2- double (phenyl oxalamide)-ethane, N, N ' -
1,2- double (phenyl oxalamide)-butane, N, N ' -1,2- double (phenyl oxalamide)-octane, decanedioic acid dibenzoyl hydrazine, N,
N ' -1,2- double (phenyl oxalamide)-hexane, N, N ' -1,2- double (phenyl oxalamide)-decane, N, the double (hexamethylenes of N ' -1,2-
Base oxalamide)-ethane, N, N ' -1,2- double (benzyl oxalamide)-ethane, N, N ' -1,2- double (n-hexyl oxalamides) -
Ethane, N '-(3- (diazanyl epoxide) benzoyl) -1- naphthalene formylhydrazines, N1,N1’,N1The third triamidos of "-(1,2,3-)-three N2- benzene
Three oxamides of base, N1,N1’,N1The third triamidos of "-(1,2,3-)-three N2Three oxamides of-ethyl acetate base, N1,N1’,N1”-(1,3,
5- triamido cyclohexyl)-three N2Three oxamides of-benzyl.
Alternatively, the shearing to composition or mixture can be realized by one of in the following manner：
(1) flowed by melt extrusion in screw extruder barrel；
(2) melt is at a high speed by narrow and small mouth mold or gap；
(3) relative movement between parallel-plate；
(4) melt extensional flow.
Alternatively, methods described can be used for the extrusion molding of the polymer, injection mo(u)lding, biaxial tension and be blow molded into
Type.
Additionally, can also be containing the filler, hydrolysis-resisting agent, antioxidant, coloring that total weight parts are 0～30 in the composition
At least one in agent and fire retardant.
From the above it can be seen that the polymer has preferable compatibility with nucleator, can be in the first temperature
Lower dissolving is partially dissolved in composition, and separates out fibrous nucleator crystal in temperature-fall period, when being cooled to second temperature
Polymeric matrix is still in unformed state.Apply nucleator and polymer molecular chain generation orientation after shearing, but be polymerized
Thing very quick returns to random coil state due to molecule chain relaxation, therefore shears little to crystallizing facilitation；Due to nucleator point
Hydrogen bond can be produced between amide group and polymer molecule in son, therefore after shearing at high temperature, the nucleator can
The relaxation of polymer molecular chain is hindered by intermolecular hydrogen bonding effect, therefore polymer molecule is in organic nucleating agent fiber
Shape microporous surface ordered arrangement, can form substantial amounts of shishi-kebab structures, there is provided extra nucleus, polymer is quickly tied
It is brilliant.It can be seen that, the nucleator causes polymer rapid crystallization with the cooperative effect of shearing.
Under a kind of high temperature that the present invention is provided, the method for polymer rapid crystallization is easily in conventional polymer material processing plant
Upper realization, is suitable for wide, low cost, easily realizes industrialized production.Additionally, some other components of addition, such as filler, coloring
Agent, processing aid etc. do not interfere with the basic crystal property of the polymeric material.
Description of the drawings：
Fig. 1 is the energy storage of embodiments of the invention 1 and 1～3 resulting composition material isothermal rheology test process of comparative example
Modulus-time graph.
Specific embodiment
Embodiment 1-11 and comparative example 1-3 is given below to be specifically described to the present invention, but is necessary here
It is pointed out that following examples are only used for being further described the present invention, it is impossible to be interpreted as the limit to the scope of the present invention
System, the person skilled in the art in the field still belong to according to some nonessential modifications and adaptations that present invention is made to the present invention
Protection scope of the present invention.
Embodiment 1
Dried N, N ' -1, double (phenyl the oxalamide)-ethane of 2- and PLA (4032D) are weighed, in mass ratio
0.5/99.5 be added in torque rheometer, after melt blending 4min being carried out under the conditions of 180 DEG C and 50rpm, gained is combined
Thing is warming up to 240 DEG C by rotational rheometer, makes N, N ' -1, double (phenyl the oxalamide)-ethane of 2- be dissolved completely in PLA
In, constant temperature 2min, then be cooled to 155 DEG C with 5 DEG C/min and apply shearing (shear rate as 0.4rad/s, shear time 5s), with
Isothermal crystal test is carried out in the temperature afterwards, flexible chain (t is calculated by rheological curve1/2), sample after test is passed through
DSC characterizes its degree of crystallinity, and test result is listed in table 1.
Embodiment 2
Dried N, N ' -1, double (phenyl the oxalamide)-butane of 2- and PLA (4032D) are weighed, in mass ratio
0.5/99.5 be added in torque rheometer, after melt blending 4min being carried out under the conditions of 180 DEG C and 50rpm, gained is combined
Thing is warming up to 200 DEG C on rotational rheometer, N, N ' double (phenyl the oxalamide)-butane of -1,2- is dissolved completely in PLA,
Constant temperature 2min, then be cooled to 155 DEG C with 5 DEG C/min and apply shearing (shear rate as 0.4rad/s, shear time 5s), subsequently exist
The temperature carries out isothermal crystal test, calculates flexible chain (t by rheological curve1/2), after testing, sample passes through DSC tables
Its degree of crystallinity is levied, test result is listed in table 1.
Embodiment 3
Weigh dried N, double (phenyl the oxalamide)-butane of N ' -1,2- and polyhydroxybutyrate-valerate copolymer
(PHBV), 0.8/99.2 is added in torque rheometer in mass ratio, under the conditions of 160 DEG C and 50rpm carries out melt blending
After 4min, resulting composition being warming up to into 200 DEG C on rotational rheometer, N, N ' double (phenyl the oxalamide)-butane of -1,2- is complete
CL in PLA, constant temperature 2min, then with 5 DEG C/min be cooled to 120 DEG C apply shearing (shear rate as 0.5rad/s,
Shearing 20s), subsequently isothermal crystal test is carried out in the temperature, flexible chain (t is calculated by rheological curve1/2), will test
Sample characterizes its degree of crystallinity by DSC afterwards, and test result is listed in table 1.
Embodiment 4
Weigh dried N, double (phenyl the oxalamide)-octanes of N ' -1,2- and polyhydroxybutyrate-valerate copolymer
(PHBV) (PHBV), 0.75/99.25 is added in torque rheometer in mass ratio, is melted under the conditions of 160 DEG C and 50rpm
Resulting composition is passed through rotational rheometer by 160 DEG C with 5 DEG C/min's by the composition being uniformly mixed after melting blending 4min
Speed is cooled to 120 DEG C and applies shearing (shear rate is 5rad/s, shears 30s), subsequently carries out isothermal crystal survey in the temperature
Examination, calculates flexible chain (t by rheological curve1/2), sample after test is characterized into its degree of crystallinity, test result row by DSC
Enter in table 1.
Embodiment 5
Weigh dried decanedioic acid dibenzoyl hydrazine, adipic acid-butylene terephthalate copolymer and PLA
(4032D), 0.5/5/94.5 is added in torque rheometer in mass ratio, under the conditions of 180 DEG C and 50rpm carries out melt blending
After 4min, resulting composition is warming up to into 240 DEG C on rotational rheometer, decanedioic acid dibenzoyl hydrazine is dissolved completely in PLA
In, constant temperature 2min, then 150 DEG C of applying shearings (shear rate shears 5s as 0.4rad/s) are cooled to 5 DEG C/min, subsequently exist
The temperature carries out isothermal crystal test, calculates flexible chain (t by rheological curve1/2), after testing, sample passes through DSC tables
Its degree of crystallinity is levied, test result is listed in table 1.
Embodiment 6
Weigh dried N, N ' -1,2- double (phenyl oxalamide)-butane, poly butyric ester (PHB) and PLAs
(4032D), the premixs of 0.8/5/94.2 in mass ratio, are then added in injection machine hopper, and barrel and extruder temperature are 18～200
DEG C, resulting composition after melt blending is sheared by cast gate and injects the mould that mould temperature is 150 DEG C by screw speed 100rpm
In tool, resulting product is carried out DSC tests by pressurize 3min, and its degree of crystallinity test result is listed in table 1.
Embodiment 7
Weigh dried adipic acid dibenzoyl hydrazine and polyethylene terephthalate (PET), in mass ratio 1/99
It is added in torque rheometer, after carrying out melt blending 4min under the conditions of 250 DEG C and 50rpm, by resulting composition in rotation
250 DEG C are warming up on flow graph, adipic acid dibenzoyl hydrazine is dissolved completely in PLA, constant temperature 2min, then dropped with 5 DEG C/min
Temperature applies shearing (shear rate is 0.4rad/s, shears 5s) to 200 DEG C, subsequently carries out isothermal crystal test in the temperature, leads to
Cross rheological curve and calculate flexible chain (t1/2), sample after test is characterized into its degree of crystallinity by DSC, test result lists table 1 in
In.
Embodiment 8
Weigh dried N '-(3- (diazanyl epoxide) benzoyl) -1- naphthalenes formylhydrazine and polypropylene, in mass ratio 1/99
It is added in torque rheometer, after carrying out melt blending 4min under the conditions of 180 DEG C and 50rpm, by resulting composition in rotation
200 DEG C are warming up on flow graph, N '-(3- (diazanyl epoxide) benzoyl) -1- naphthalene formylhydrazines are dissolved completely in polypropylene, it is permanent
Warm 2min, then 160 DEG C of applying shearings (shear rate shears 10s as 0.4rad/s) are cooled to 5 DEG C/min, subsequently in the temperature
Degree carries out isothermal crystal test, calculates flexible chain (t by rheological curve1/2), sample after test is characterized into which by DSC
Degree of crystallinity, test result are listed in table 1.
Embodiment 9
Dried N, N ' -1, double (phenyl the oxalamide)-ethane of 2- and ethylene-propylene copolymer are weighed, in mass ratio
1/99 is added in torque rheometer, after carrying out melt blending 4min, resulting composition is existed under the conditions of 180 DEG C and 50rpm
250 DEG C being warming up on rotational rheometer, N, N ' double (phenyl the oxalamide)-ethane of -1,2- is dissolved completely in ethylene-propylene copolymer
In thing, constant temperature 2min, then 155 DEG C of applying shearings (shear rate shears 5s as 0.4rad/s) are cooled to 5 DEG C/min, subsequently
Isothermal crystal test is carried out in the temperature, flexible chain (t is calculated by rheological curve1/2), after testing, sample passes through DSC
Its degree of crystallinity is characterized, test result is listed in table 1.
Embodiment 10
Dried N, N ' -1, double (phenyl the oxalamide)-ethane of 2- and PLA (4032D) are weighed, in mass ratio
0.5/99.5 be added in torque rheometer, be uniformly mixed after melt blending 4min being carried out under the conditions of 180 DEG C and 50rpm
Composition, resulting composition is cooled to into 155 DEG C applyings from 180 DEG C of speed with 5 DEG C/min by rotational rheometer then
Shearing (shear rate is 0.4rad/s, shear time 5s), subsequently carries out isothermal crystal test in the temperature, by rheological curve
Calculate flexible chain (t1/2), sample after test is characterized into its degree of crystallinity by DSC, test result is listed in table 1.
Embodiment 11
Dried N, N ' -1, double (phenyl the oxalamide)-butane of 2- and PLA (4032D) are weighed, in mass ratio
0.5/99.5 be added in torque rheometer, be uniformly mixed after melt blending 4min being carried out under the conditions of 180 DEG C and 50rpm
Composition, resulting composition is warming up to into 200 DEG C by rotational rheometer then, is then cooled to the speed of 5 DEG C/min
155 DEG C apply shearing (shear rate is 0.5rad/s, shear time 10s), subsequently carry out isothermal crystal test in the temperature, lead to
Cross rheological curve and calculate flexible chain (t1/2), sample after test is characterized into its degree of crystallinity by DSC, test result lists table 1 in
In.
Comparative example 1
Dried PLA (4032D) is weighed, is added in torque rheometer, at 180 DEG C, under the conditions of rotating speed 50rpm
After carrying out melt blending 4min, gained PLA is warming up to into 200 DEG C on rotational rheometer, constant temperature 2min, then with 5 DEG C/min
155 DEG C are cooled to, do not apply shearing, subsequently isothermal crystal rheometer test is carried out in the temperature, and calculate half by rheological curve
Crystallization time (t1/2), sample after test is carried out into DSC signs, every test result is listed in table 1.
Comparative example 2
Dried PLA (4032D) is weighed, is added in torque rheometer, at 180 DEG C, under the conditions of rotating speed 50rpm
After carrying out melt blending 4min, resulting composition is warming up to into 200 DEG C on rotational rheometer, constant temperature 2min, then with 5 DEG C/min
Be cooled to 155 DEG C and apply shearing (shear rate is 0.4rad/s, shears 5s), subsequently isothermal crystal rheology survey is carried out in the temperature
Examination, calculates flexible chain (t by rheological curve1/2), sample after test is carried out into DSC signs, every test result lists table in
In 1.
Comparative example 3
Dried N, N ' -1, double (phenyl the oxalamide)-ethane of 2- and PLA (4032D) are weighed, in mass ratio
0.5/99.5 it is added in torque rheometer, at 180 DEG C, after carrying out melt blending 4min under the conditions of rotating speed 50rpm, by gained group
Compound is warming up to 240 DEG C on rotational rheometer, and nucleator is dissolved completely in PLA, constant temperature 2min, then is dropped with 5 DEG C/min
Temperature does not apply shearing, subsequently carries out isothermal crystal rheometer test in the temperature, calculate hypocrystalline by rheological curve to 155 DEG C
Time (t1/2), sample after test is carried out into DSC signs, every test result is listed in table 1.
It should be noted that polymer used and amide-type nucleator are existed using front in various embodiments above and comparative example
It is vacuum dried 12 hours at 50 DEG C.PLA used be U.S. Natureworks LLC Products PLA 4032D, fusing point
For 175 DEG C, glass transition temperature is 56 DEG C；PHA used is Ningbo Tianan Biological Material Co., Ltd.'s product,
Wherein in copolymer, valeric acid ester content is about 8%, about 150 DEG C of fusing point；Adipic acid used-butylene terephthalate copolymer
For Zhejiang Xin Fu pharmaceutcal corporation, Ltds product, polyethylene terephthalate used is du pont company's product, used
Amides compound be commercially available or laboratory made products, purity>95%.
Above-mentioned rheometer test is characterized, controlled strain 1%, frequency 1Hz, the energy storage mould of test polymer or polymer composition
Amount, tests its sample flexible chain t at different temperatures1/2。
Above-mentioned differential scanning calorimeter (DSC) characterize step be by rheometer test after (or after injection mo(u)lding) polymer or
Polymer composition from room temperature with more than the ramp of 10 DEG C/min to melting point polymer 30 DEG C, according to polymer or polymer
The melting enthalpy of composition is tested and calculates the crystallinity X of polymerc。
The performance parameter of polymeric material in 1 embodiment of table and comparative example
Note：There is no substantially crystallization with the testing time (90min) at test temperature in comparative example 1～3；Embodiment 6 is
Injected sample, its forming process flexible chain fail actually measured.
As can be seen from the above table, comparative example 1～3 is not crystallized substantially in test temperature and in the testing time, by contrast, real
Apply the flexible chain t of 1～11 gained polyester of example and polyolefine material1/2Within shortening to 25min, degree of crystallinity is brought up to by 0%
About more than 40%.It can be seen that, the technology of the present invention is improve with the synergy of threadiness/needle-like organic nucleating agent by shearing and is polymerized
The crystalline rate and degree of crystallinity of thing, can give polymeric material excellent physical mechanical performance and heat resistance etc..Additionally, embodiment 1,
Embodiment 3, embodiment 4 and embodiment 10 are completely dissolved it is also shown that the composition obtained by melt blending is warming up to nucleator
Lower the temperature after in the polymeric matrix again applying shearing, the flexible chain of polymer is shorter, degree of crystallinity is higher.This is because, into
Core agent forms homogeneous system after being dissolved completely in polymeric matrix, and in follow-up cooling procedure, nucleation agent molecule being capable of self assembly
Become be more evenly distributed, smaller microfibrillar structure, the special construction specific surface area increases, after the shearing can by point
Between son, hydrogen bond action effectively suppresses the lax of oriented polymer molecules, so as to remarkably promoting the original nucleation of polymer and crystallizing
Journey.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the specific embodiment of foregoing description, all spirit in the present invention be the invention is not limited in
Within principle, any modification, equivalent substitution and improvements done etc. should be included within the scope of the present invention.
Claims (10)
1. under a kind of polymer high temperature polymer rapid crystallization method, it is characterised in that methods described includes walking in detail below
Suddenly：
(1) by polymer, melt blending obtains finely dispersed combination at the first temperature by weight ratio with organic nucleating agent
Thing；
(2) above-mentioned composition is warming up to nucleator to be dissolved completely in polymer, forms homogeneous mixture；
(3) apply shearing to the homogeneous mixture that above-mentioned (2) obtain at the second temperature, you can promote polymer rapid crystallization.
2. under a kind of polymer high temperature rapid crystallization method, it is characterised in that methods described includes step in detail below：
(1) by polymer, melt blending obtains finely dispersed combination at the first temperature by weight ratio with organic nucleating agent
Thing；
(2) apply shearing to above-mentioned composition at the second temperature, you can promote polymer rapid crystallization.
3. the method for a kind of polymer rapid crystallization according to claim 1 and 2, it is characterised in that the polymer is
It is PLA, polyhydroxyalkanoate, poly butylene succinate, adipic acid-butylene terephthalate copolymer, poly- to benzene two
At least one in formic acid glycol ester, polybutylene terephthalate (PBT), polypropylene and propylene copolymer.
4. a kind of method of polymer rapid crystallization according to claim 1 and 2, it is characterised in that organic nucleation
Agent is at least one in the amides compound containing multiple-CONH- functional groups；In the preferred amides compound extremely
Contain 1-HNCOCONH- functional group less.
5. a kind of method of polymer rapid crystallization according to claim 1 and 2, it is characterised in that first temperature
For more than melting point polymer 1～50 DEG C, 5～30 DEG C preferably more than melting point polymer, second temperature is below melting point polymer 1
～80 DEG C, 20～50 DEG C preferably below melting point polymer；Described high temperature is second temperature.
6. a kind of method of polymer rapid crystallization according to claim 1 and 2, it is characterised in that the composition material
In material, the content of polymer is 90～99.9 weight portions, and the content of organic nucleating agent is 0.1～2 weight portion.
7. a kind of method of polymer rapid crystallization according to claim 1 and 2, it is characterised in that the composition material
Containing at least one in filler, hydrolysis-resisting agent, antioxidant, colouring agent and the fire retardant that total weight parts are 0～30 in material.
8. a kind of method of polymer rapid crystallization according to claim 1 and 2, it is characterised in that the speed of the shearing
Rate is 0.2～20rad/s, and shear time is 0.1～300s.
9. the method for a kind of polymer rapid crystallization according to claim 1 and 2, it is characterised in that described to composition
Or the shearing of mixture can be realized by one of in the following manner：
(1) flowed by melt extrusion in screw extruder barrel；
(2) melt is at a high speed by narrow and small mouth mold or gap；
(3) relative movement between parallel-plate；
(4) melt extensional flow.
10. the method for a kind of polymer rapid crystallization according to claim 1 and 2, it is characterised in that methods described can use
Extrusion molding, injection mo(u)lding, biaxial tension and blow molding in polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610952275.4A CN106519610A (en) | 2016-11-02 | 2016-11-02 | Method for rapid crystallization of polymer at high temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610952275.4A CN106519610A (en) | 2016-11-02 | 2016-11-02 | Method for rapid crystallization of polymer at high temperature |
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| CN108384200A (en) * | 2018-02-07 | 2018-08-10 | 浙江大学 | A kind of PBAT materials of rapid crystallization and preparation method thereof |
| CN108384201A (en) * | 2018-02-07 | 2018-08-10 | 浙江大学 | A kind of PBAT materials and preparation method thereof that crystallization rate is fast |
| CN112126203A (en) * | 2020-09-27 | 2020-12-25 | 江南大学 | Rapid crystallization polyester material and preparation method and application thereof |
| CN112980027A (en) * | 2021-03-09 | 2021-06-18 | 宁波大学 | Preparation method of PHBV with high mechanical property |
| CN115232451A (en) * | 2022-07-10 | 2022-10-25 | 四川大学 | Polyhydroxyalkanoate material or product capable of being crystallized rapidly and preparation method thereof |
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| CN103360682A (en) * | 2013-07-09 | 2013-10-23 | 顾建生 | Heat-insulated degradable polypropylene foaming material and production method thereof |
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| CN103717648A (en) * | 2011-10-18 | 2014-04-09 | 积水化学工业株式会社 | Method for producing resin composite material, and resin composite material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384200A (en) * | 2018-02-07 | 2018-08-10 | 浙江大学 | A kind of PBAT materials of rapid crystallization and preparation method thereof |
| CN108384201A (en) * | 2018-02-07 | 2018-08-10 | 浙江大学 | A kind of PBAT materials and preparation method thereof that crystallization rate is fast |
| CN108384200B (en) * | 2018-02-07 | 2020-04-17 | 浙江大学 | Quickly crystallized PBAT material and preparation method thereof |
| CN112126203A (en) * | 2020-09-27 | 2020-12-25 | 江南大学 | Rapid crystallization polyester material and preparation method and application thereof |
| CN112126203B (en) * | 2020-09-27 | 2022-02-15 | 江南大学 | Rapid crystallization polyester material and preparation method and application thereof |
| CN112980027A (en) * | 2021-03-09 | 2021-06-18 | 宁波大学 | Preparation method of PHBV with high mechanical property |
| CN115232451A (en) * | 2022-07-10 | 2022-10-25 | 四川大学 | Polyhydroxyalkanoate material or product capable of being crystallized rapidly and preparation method thereof |
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