CN107974052B - A kind of polymer blend and its preparation method and application - Google Patents
A kind of polymer blend and its preparation method and application Download PDFInfo
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- CN107974052B CN107974052B CN201610922101.3A CN201610922101A CN107974052B CN 107974052 B CN107974052 B CN 107974052B CN 201610922101 A CN201610922101 A CN 201610922101A CN 107974052 B CN107974052 B CN 107974052B
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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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to a kind of polymer blends and its preparation method and application.Polymer blend provided by the invention contains polyester A, polyester B and aliphatic polyester.The present invention also provides a kind of preparation methods of polymer blend, this method comprises: polyester A, polyester B and aliphatic polyester are mixed, and obtained mixture are carried out extruding pelletization, to obtain polymer blend.The present invention also provides application of the polymer blend in shape-memory material.Polymer blend provided by the invention is used for shape-memory material, the deformation fixed rate and shape recovery rate of the shape-memory material reach 92% or more, and largest deformation rate is up to 400% or more.In addition, the initial figuration temperature and start-up temperature of the shape-memory material are adjustable, this would be even more beneficial to its application in daily life.
Description
Technical field
The present invention relates to polymer arts, and in particular, to a kind of polymer blend, the preparation side of the polymer blend
Method, the application of the polymer blend being prepared by this method and the polymer blend in shape-memory material.
Background technique
Shape-memory material is a kind of special intellectual material.Shape memory metal has many in industry and life
Using, for example, Philips Corporate can only tire stud, can be extended automatically in icy road, improve the skid resistance of tire
Energy.Italian a company develops the clothes containing shape-memory material, and sleeve can automatic roll up when same day heat.In space
The antenna of some satellites is also made of shape memory type metal.Shape-memory material is most typical in terms of shape memory effect to answer
With being exactly shape memory pipe fitting.Shape memory pipe fitting can connect two pipelines, and especially two size differences are very big
Pipeline.Shape memory pipe fitting has many advantages, such as that high reliablity, structure are simple, easy for installation, saves assembly space.Shape memory
Material is often applied to particular surroundings demand, or the field of hommization, usually has the characteristics that high added value, is that one kind can not
The new material of substitution.
After thermotropic induction type shape-memory material undergoes initial figuration, deformed at a certain temperature by external force, it is cooling
After be able to maintain deformed shape；And after heating again, it can return to the original form.There is shape memory type macromolecule processing to hold
Easily, light weight, low operation temperature and the advantages such as cheap, therefore often there is it to be applied in the industry of many high added values
Research.The high molecular largest deformation rate of shape memory type is usually between 10-100%.
Shape memory type macromolecule is divided into reversible and two kinds irreversible.Irreversible shape memory type is high molecular initially
Shape can not be changed Yi Dan assigned, and reversible shape memory type macromolecule, its initial figuration is changeable, more ring
It protects.
For irreversible shape memory type high molecular material, for example, CN103160948A discloses one kind based on crosslinking
Shape memory high molecule.Its deformation fixed rate is about 90-98%, and shape recovery rate is between 85-95%.This kind of shape note
Recall high molecular initial figuration it is all not reproducible and regeneration.Also, their deformation fixed rate and shape recovery rate and 100% are all
There is a certain distance.Their largest deformation rate is usually between 20%-400%.And for reversible shape memory type high score
Son, for example, a kind of shape memory high molecule that CN105504474A is disclosed, its shape recovery rate is 80-95%, and shape is fixed
Rate is about 90-98%, and largest deformation rate is about 50%.Although initially figuration is repeatable for this kind of shape memory type macromolecule, it
Shape recovery rate and shape fixed rate be often not so good as irreversible shape memory type macromolecule, and largest deformation rate is worse
It is more, typically less than 100%.Currently on the market there is no one kind can big deformation, and shape recovery rate and shape fixed rate
All close to 100% reversible shape memory-type macromolecule.
Summary of the invention
The drawbacks described above that the purpose of the invention is to overcome existing shape memory product to have provides a kind of polyester
Composition and preparation method thereof, the polymer blend and the polymer blend be prepared by this method is in shape memory material
Application in material.
The present invention provides a kind of polymer blend, which includes:
(1) polyester A, the polyester A are to contain repetitive unit B's shown in repetitive unit A shown in formula (I) and formula (II)
Copolymer,
(2) polyester B, the polyester B are to contain repetitive unit B shown in repetitive unit C shown in formula (III) and formula (II)
Copolymer,
(3) aliphatic polyester,
Wherein, m1 is the integer of 2-10, and n1 is the integer of 2-8, and m1 and n1 are identical or different, and the weight of the polyester A is equal
Molecular weight is 50,000-900,000；M2 is the integer of 2-10, and n2 is the integer of 2-8, and m2 and n2 are identical or different, described poly-
The weight average molecular weight of ester B is 50,000-900,000；Also, n1 is less than n2；
On the basis of the total mole number of the polyester A, the polyester B and the aliphatic polyester, the repetitive unit B's
Content is 5-49 moles of %.
The present invention also provides a kind of preparation methods of polymer blend, which is characterized in that this method comprises: by polyester A,
Polyester B and aliphatic polyester mixing, and obtained mixture is subjected to extruding pelletization, to obtain polymer blend；
The polyester A is the copolymer containing repetitive unit B shown in repetitive unit A shown in formula (I) and formula (II),
The polyester B is the copolymer containing repetitive unit B shown in repetitive unit C shown in formula (III) and formula (II),
Wherein, m1 is the integer of 2-10, and n1 is the integer of 2-8, and m1 and n1 are identical or different, and the weight of the polyester A is equal
Molecular weight is 50,000-900,000；M2 is the integer of 2-10, and n2 is the integer of 2-8, and m2 and n2 are identical or different, described poly-
The weight average molecular weight of ester B is 50,000-900,000；Also, n1 is less than n2；
On the basis of the total mole number of the polyester A, the polyester B and the aliphatic polyester, the repetitive unit B's
Content is 5-49 moles of %.
The present invention also provides polymer blends prepared by the above method.
The present invention also provides application of the above-mentioned polymer blend in shape-memory material.
The present invention has been obtained a kind of suitable by being copolymerized to polybutylene terephthalate (PBT) (PBT) and blending and modifying
For being used as the polymer blend of shape-memory material.The polymer blend is used for shape-memory material, the shape memory material
The deformation fixed rate and shape recovery rate of material reach 92% or more, and largest deformation rate is up to 400% or more.In addition, the shape
The initial figuration temperature and start-up temperature of memory material are adjustable, this would be even more beneficial to its application in daily life.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of polymer blend, which includes:
(1) polyester A, the polyester A are to contain repetitive unit B's shown in repetitive unit A shown in formula (I) and formula (II)
Copolymer,
(2) polyester B, the polyester B are to contain repetitive unit B shown in repetitive unit C shown in formula (III) and formula (II)
Copolymer,
(3) aliphatic polyester,
Wherein, m1 is the integer of 2-10, and n1 is the integer of 2-8, and m1 and n1 are identical or different, and the weight of the polyester A is equal
Molecular weight is 50,000-900,000；M2 is the integer of 2-10, and n2 is the integer of 2-8, and m2 and n2 are identical or different, described poly-
The weight average molecular weight of ester B is 50,000-900,000；Also, n1 is less than n2；With the polyester A, the polyester B and the fat
On the basis of the total mole number of adoption ester, the content of the repetitive unit B is 5-49 moles of %.
In situations where it is preferred, m1 is the integer of 2-6, n1 is the integer of 2-4, and m1 and n1 are identical or different, described poly-
The weight average molecular weight of ester A is 100,000-500,000；M2 is the integer of 2-6, and n2 is the integer of 2-4, and m2 and n2 is identical or not
Together, the weight average molecular weight of the polyester B is 100,000-500,000；Also, n1 is less than n2；With the polyester A, the polyester B
On the basis of the total mole number of the aliphatic polyester, the content of the repetitive unit B is 5-49 moles of %, preferably 20-40
Mole %, more preferably 25-40 moles of %.
In the present invention, the weight average molecular weight of polymer is measured according to gel permeation chromatography (GPC).
In the present invention, the polyester A can be random copolymer, alternate copolymer, block copolymer and graft copolymerization
At least one of object, preferably random copolymer and/or block copolymer.The present invention is to the source of the polyester A without spy
Other restriction can be obtained by the conventional means of this field, for example, can be commercially available, alternatively, can be according to
Method disclosed in CN100429256C is prepared.Specifically, the preparation method of the polyester A may comprise steps of:
1,4-butanediol, benzoic acid dimethyl ester and the catalyst as described in US11312373 are added in reactor, in nitrogen atmosphere
Lower heating and stirring, until obtaining transparent solution.Then, temperature is risen into 160-220 DEG C of reaction.When most in system
After the methanol distilled out is removed, succinic acid is added, is warming up to 180-240 DEG C.Most of water is distilled off, then slowly adds
Vacuum environment, and react and complete after system is warming up to 220-280 DEG C, 3-6 hours, obtain product.
In the present invention, the polyester B can be random copolymer, alternate copolymer, block copolymer and graft copolymerization
At least one of object, preferably random copolymer and/or block copolymer.The present invention is to the source of the polyester B without spy
Other restriction can be obtained by the conventional means of this field, for example, can be commercially available, alternatively, can be according to
Method disclosed in CN100429256C is prepared.Specifically, the preparation method of the polyester B may comprise steps of:
1,4-butanediol, benzoic acid dimethyl ester and the catalyst as described in US11312373 are added in reactor, in nitrogen atmosphere
Lower heating and stirring, until obtaining transparent solution.Then, temperature is risen into 160-220 DEG C of reaction.When most in system
After the methanol distilled out is removed, adipic acid is added, is warming up to 180-240 DEG C.Most of water is distilled off, then slowly adds
Vacuum environment, and react and complete after system is warming up to 220-280 DEG C, 3-6 hours, obtain product.
According to the present invention, on the basis of the total mole number of repetitive unit A and repetitive unit B in the polyester A, the repetition
The content of unit A can be 40-95 moles of %, preferably 45-90 moles of %, more preferably 45-70 moles of %；It is described to repeat list
The content of first B can be 5-60 moles of %, preferably 10-55 moles of %, more preferably 30-55 moles of %；
On the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B, the content of the repetitive unit C
It can be 40-95 moles of %, preferably 50-90 moles of %, more preferably 50-80 moles of %；The content of the repetitive unit B can
Think 5-60 moles of %, preferably 10-50 moles of %, more preferably 20-50 moles of %.
According to the present invention, the molar ratio of the polyester A, the polyester B and the aliphatic polyester can be 20-90:1-
90:1-20；Preferably 20-90:1-70:1-20.
In the present invention, to the type of the aliphatic polyester, there is no particular limitation, can be commonly used in the art
Aliphatic polyester.
In situations where it is preferred, the aliphatic polyester contains repetitive unit D shown in formula (VI),
Wherein, m3 is the integer of 2-10, and n3 is the integer of 2-8, and m3 and n3 are identical or different, the aliphatic polyester
Weight average molecular weight is 50,000-900,000；It is highly preferred that m3 is the integer of 2-6, n3 is the integer of 2-4, and m3 and n3 is identical
Or it is different, the weight average molecular weight of the aliphatic polyester is 100,000,500,000.
In the present invention, the aliphatic polyester can be obtained by conventional means, for example, can be commercially available
(as being purchased from BASF AG, trade mark 1111HTA4), alternatively, can be prepared into according to method disclosed in CN104039865B
It arrives, wherein the type of reaction raw materials can correspondingly be adjusted according to the composition and molecular weight of target product, and by adjusting
Inventory and feed ratio control the content of each repetitive unit in the molecular weight and product of product respectively.
According to the present invention, the polymer blend can also contain nucleating agent；Total weight with the polymer blend is
Benchmark, the content of the nucleating agent are 0.01-10 weight %, preferably 0.2-5 weight %, more preferably 1-5 weight %.
According to the present invention, the nucleating agent can be the conventional selection of this field, for example, the nucleating agent can be selected from cunning
Mountain flour, calcium oxide, carbon black, calcium carbonate, inorganic pigment are (such as the yellow or green face purchased from Guangzhou Ying Yi plastic pigment Co., Ltd
Material), kaolin, carboxylic metallic salt, phosphate metal salt, dibenzyl sorbierite and its derivative, polyvinyl eyclohexane, polyethylene penta
One or more of alkane, low density polyethylene (LDPE), ultrabranching polyamide and ethylene-methyl methacrylate ionomer；Preferably carbonic acid
Calcium, low density polyethylene (LDPE), dibenzyl sorbierite and its one or more of derivative and ultrabranching polyamide；More preferably carbonic acid
Calcium and/or low density polyethylene (LDPE).
In the present invention, the polymer blend can also contain other additives, such as can also contain erucyl amide
And/or white oil.
The present invention also provides a kind of preparation methods of polymer blend, this method comprises: by polyester A, polyester B and fat
The mixing of adoption ester, and obtained mixture is subjected to extruding pelletization, to obtain polymer blend；
The polyester A is the copolymer containing repetitive unit B shown in repetitive unit A shown in formula (I) and formula (II),
The polyester B is the copolymer containing repetitive unit B shown in repetitive unit C shown in formula (III) and formula (II),
Wherein, m1 is the integer of 2-10, and n1 is the integer of 2-8, and m1 and n1 are identical or different, and the weight of the polyester A is equal
Molecular weight is 50,000-900,000；M2 is the integer of 2-10, and n2 is the integer of 2-8, and m2 and n2 are identical or different, described poly-
The weight average molecular weight of ester B is 50,000-900,000；Also, n1 is less than n2；With the polyester A, the polyester B and the fat
On the basis of the total mole number of adoption ester, the content of the repetitive unit B is 5-49 moles of %.
In situations where it is preferred, m1 is the integer of 2-6, n1 is the integer of 2-4, and m1 and n1 are identical or different, described poly-
The weight average molecular weight of ester A is 100,000-500,000；M2 is the integer of 2-6, and n2 is the integer of 2-4, and m2 and n2 is identical or not
Together, the weight average molecular weight of the polyester B is 100,000-500,000；Also, n1 is less than n2；With the polyester A, the polyester B
On the basis of the total mole number of the aliphatic polyester, the content of the repetitive unit B is 10-45 moles of %, preferably 20-40
Mole %, more preferably 35-45 moles of %.
In the present invention, the polyester A can be random copolymer, alternate copolymer, block copolymer and graft copolymerization
At least one of object, preferably random copolymer and/or block copolymer.The present invention is to the source of the polyester A without spy
Other restriction can be obtained by the conventional means of this field, and as detailed above, details are not described herein.
In the present invention, the polyester B can be random copolymer, alternate copolymer, block copolymer and graft copolymerization
At least one of object, preferably random copolymer and/or block copolymer.The present invention is to the source of the polyester B without spy
Other restriction can be obtained by the conventional means of this field, and as detailed above, details are not described herein.
According to the present invention, on the basis of the total mole number of repetitive unit A and repetitive unit B in the polyester A, the repetition
The content of unit A can be 40-95 moles of %, preferably 45-90 moles of %, more preferably 45-70 moles of %；It is described to repeat list
The content of first B can be 5-60 moles of %, preferably 10-55 moles of %, more preferably 30-55 moles of %；
On the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B, the content of the repetitive unit C
It can be 40-95 moles of %, preferably 50-90 moles of %, more preferably 50-80 moles of %；The content of the repetitive unit B can
Think 5-60 moles of %, preferably 10-50 moles of %, more preferably 20-50 moles of %.
According to the present invention, the molar ratio of the dosage of the polyester A, the polyester B and the aliphatic polyester can be 20-
90:1-90:1-20；Preferably 20-90:1-70:1-20.
In the present invention, the type of the aliphatic polyester and source can be the conventional selection of this field, specific as above
Described, details are not described herein.
According to the present invention, the above method can also include: to mix polyester A, polyester B, aliphatic polyester and nucleating agent
Process carries out in the presence of nucleating agent；On the basis of the total weight of the polymer blend, the dosage of the nucleating agent can be with
For 0.01-20 weight %, preferably 0.2-5 weight %.
According to the present invention, the nucleating agent can be the conventional selection of this field, for example, the nucleating agent can be selected from cunning
Mountain flour, calcium oxide, carbon black, calcium carbonate, inorganic pigment are (such as the yellow or green face purchased from Guangzhou Ying Yi plastic pigment Co., Ltd
Material), kaolin, carboxylic metallic salt, phosphate metal salt, dibenzyl sorbierite and its derivative, polyvinyl eyclohexane, polyethylene penta
One or more of alkane, low density polyethylene (LDPE), ultrabranching polyamide and ethylene-methyl methacrylate ionomer；Preferably carbonic acid
Calcium, low density polyethylene (LDPE), dibenzyl sorbierite and its one or more of derivative and ultrabranching polyamide；More preferably carbonic acid
Calcium and/or low density polyethylene (LDPE).
In the present invention, the above method can also include: to mix polyester A, polyester B, aliphatic polyester and nucleating agent
Process is carried out in nucleating agent and other additives in the presence ofs, wherein other described additives can be erucyl amide and/or white
Oil.
According to the present invention, the mixing can carry out under stirring conditions；The rate of the stirring can be 6-
60rpm, the time of the stirring can be 2-30min.
According to the present invention, the extruding pelletization process can be implemented according to conventional extruding pelletization method, for example, described squeeze
Being granulated out can carry out in double screw extruder；Preferably, it is 160-220 DEG C that the condition of the extruding pelletization, which includes: temperature,
Screw speed is 10-70rpm, torque 2-80N*m；It is highly preferred that the double screw extruder includes six temperature sections, and
From feed inlet to extrusion the temperature of each section be followed successively by 160-190 DEG C, 170-200 DEG C, 180-210 DEG C, 180-220 DEG C,
180-220℃、170-210℃。
The present invention also provides application of the above-mentioned polymer blend in shape-memory material.
The present invention has been obtained a kind of suitable by being copolymerized to polybutylene terephthalate (PBT) (PBT) and blending and modifying
For being used as the polymer blend of shape-memory material.The polymer blend is used for shape-memory material, the shape memory material
For the deformation fixed rate and shape recovery rate of material close to 100%, largest deformation rate is up to 400% or more.In addition, the shape memory
The initial figuration temperature and start-up temperature of material are adjustable, this would be even more beneficial to its application in daily life.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, the weight average molecular weight of polymer uses gel permeation chromatography (GPC), with four
Hydrogen furans (THF) is solvent, in Waters-208 (band Waters 2410RI detector, 1.5mL/min flow velocity, 30 DEG C) instrument
Upper measurement, with the calibration of styrene standard specimen；
The microstructure of polyester A, polyester B and aliphatic polyester use the AVANCE DRX of Switzerland Bruker company
400MHz nuclear magnetic resonance chemical analyser measurement, using deuterated chloroform as solvent；
The composition of polymer blend passes through the determination that feeds intake of raw material；
The shape changing memory performance of polymer blend is specific as follows using Instron5965 tensilometer (band insulating box) measurement:
The initial length of polymer blend batten at room temperature is a；Insulating box is warming up to 80 DEG C, softens it sufficiently,
Length b is stretched under conditions of tensile speed is 50mm/min；It keeps external force to keep tensile elongation constant, cools down, it is solid to batten
Change, remove external force, the length of batten is c at this time；It batten is warming up to 80 DEG C again, sufficiently bounces back to batten, at this time batten
Length is d；
Deformation fixed rate (%)=(c-a)/(b-a) × 100%；
Shape recovery rate (%)=(c-d)/(c-a) × 100%；
Largest deformation rate (%)=bmax/ a × 100%, wherein bmaxAttainable maximum b value before being damaged for batten；
In case of no particular description, the aliphatic-aromatic copolyester that the present invention uses according to
Method disclosed in embodiment B13-B21 is voluntarily prepared in CN100429256C, wherein can be according to the composition of target product
And molecular weight, the type of reaction raw materials is correspondingly adjusted, and control point of product respectively by adjusting inventory and feed ratio
The content of each repetitive unit in son amount and product.
Embodiment 1
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 10min) under stirring conditions, by terephthalic acid (TPA) butanediol-fourth two
Sour butanediol copolyester (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and succinic acid fourth
On the basis of the total mole number of diol repeat units, the content of terephthalic acid (TPA) butanediol repetitive unit is 30 moles of %), to benzene two
Formic acid butanediol-adipic acid butanediol copolyester (is purchased from BASF AG, trade mark ecoflex, wherein with terephthalic acid (TPA)
On the basis of the total mole number of butanediol repetitive unit and adipic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol repetitive unit
Content be 50 moles of %) and poly butylene succinate (purchased from BASF AG, trade mark 1111HTA4) according to 40:40:
20 molar ratio is mixed, and 1 weight % calcium carbonate is added (on the basis of the total weight of mixture).The mixture that will be obtained
Extruding pelletization is carried out by double screw extruder, the revolving speed control of screw rod is 10rpm, torque 20N*m, in double screw extruder
The temperature of each section is followed successively by 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 220 DEG C, 210 DEG C from feed inlet to extrusion, is made poly-
Ester composition A1.
Comparative example 1
Polymer blend is prepared according to the method for embodiment 1, the difference is that using the poly- terephthaldehyde of same molar
Sour butanediol ester (being purchased from E.I.Du Pont Company, the trade mark is by Crastin SC164NC010) replaces terephthaldehyde used in embodiment 1
Polymer blend D1 is made in sour butanediol-succinic acid butanediol copolyester.
Comparative example 2
Polymer blend is prepared according to the method for embodiment 1, the difference is that using the poly- terephthaldehyde of same molar
Sour butanediol ester (being purchased from E.I.Du Pont Company, the trade mark is by Crastin SC164NC010) replaces terephthaldehyde used in embodiment 1
Polymer blend D2 is made in sour butanediol-adipic acid butanediol copolyester.
Comparative example 3
Polymer blend is prepared according to the method for embodiment 1, the difference is that being added without poly- fourth used in embodiment 1
Polymer blend D3 is made in succinate adipate.
Comparative example 4
Polymer blend is prepared according to the method for embodiment 1, the difference is that terephthalic acid (TPA) butanediol-succinic acid fourth
Glycol copolyesters, terephthalic acid (TPA) butanediol-adipic acid butanediol copolyester and poly butylene succinate are according to 2:2:96's
Molar ratio is mixed, and polymer blend D4 is made.
Embodiment 2
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 10min) under stirring conditions, by terephthalic acid (TPA) butanediol-fourth two
Sour butanediol copolyester (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and succinic acid fourth
On the basis of the total mole number of diol repeat units, the content of terephthalic acid (TPA) butanediol repetitive unit is 55 moles of %), to benzene two
Formic acid butanediol-adipic acid butanediol copolyester (weight average molecular weight 100,000, wherein with the repetition of terephthalic acid (TPA) butanediol
On the basis of the total mole number of unit and adipic acid butanediol repetitive unit, the content of terephthalic acid (TPA) butanediol repetitive unit is 20
Mole %) and poly butylene succinate mixed according to the molar ratio of 20:70:10, and be added 1 weight % calcium carbonate (with
On the basis of the total weight of mixture).Obtained mixture is subjected to extruding pelletization, the revolving speed control of screw rod by double screw extruder
Be made as 10rpm, torque 20N*m, in double screw extruder from feed inlet to extrusion the temperature of each section be followed successively by 190 DEG C,
Polymer blend A2 is made in 200 DEG C, 210 DEG C, 220 DEG C, 220 DEG C, 210 DEG C.
Embodiment 3
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 10min) under stirring conditions, by terephthalic acid (TPA) butanediol-fourth two
Sour butanediol copolyester (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and succinic acid fourth
On the basis of the total mole number of diol repeat units, the content of terephthalic acid (TPA) butanediol repetitive unit is 30 moles of %), to benzene two
Formic acid butanediol-adipic acid butanediol copolyester (is purchased from BASF AG, trade mark ecoflex, wherein with terephthalic acid (TPA)
On the basis of the total mole number of butanediol repetitive unit and adipic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol repetitive unit
Content be 50 moles of %) and poly butylene succinate mixed according to the molar ratio of 50:49:1, and addition 1 weight %
Calcium carbonate (on the basis of the total weight of mixture).Obtained mixture is subjected to extruding pelletization, spiral shell by double screw extruder
The revolving speed control of bar is 10rpm, torque 20N*m, in double screw extruder from feed inlet to extrusion each section temperature according to
It is secondary be 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, be made polymer blend A3.
Embodiment 4
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 10min) under stirring conditions, by terephthalic acid (TPA) butanediol-fourth two
Sour butanediol copolyester (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and succinic acid fourth
On the basis of the total mole number of diol repeat units, the content of terephthalic acid (TPA) butanediol repetitive unit is 40 moles of %), to benzene two
Formic acid butanediol-adipic acid butanediol copolyester (is purchased from BASF AG, trade mark ecoflex, wherein with terephthalic acid (TPA)
On the basis of the total mole number of butanediol repetitive unit and adipic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol repetitive unit
Content be 50 moles of %) and poly butylene succinate mixed according to the molar ratio of 90:1:9, and addition 1 weight % carbon
Sour calcium (on the basis of the total weight of mixture).Obtained mixture is subjected to extruding pelletization, screw rod by double screw extruder
Revolving speed control be 10rpm, torque 20N*m, the temperature of each section is successively from feed inlet to extrusion in double screw extruder
For 160 DEG C, 170 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 170 DEG C, polymer blend A4 is made.
Embodiment 5
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 10min) under stirring conditions, by terephthalic acid (TPA) butanediol-fourth two
Sour butanediol copolyester (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and succinic acid fourth
On the basis of the total mole number of diol repeat units, the content of terephthalic acid (TPA) butanediol repetitive unit is 40 moles of %), to benzene two
Formic acid butanediol-adipic acid butanediol copolyester (is purchased from BASF AG, trade mark ecoflex, wherein with terephthalic acid (TPA)
On the basis of the total mole number of butanediol repetitive unit and adipic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol repetitive unit
Content be 50 moles of %) and poly butylene succinate mixed according to the molar ratio of 90:1:9, and addition 5 weight % carbon
Sour calcium (on the basis of the total weight of mixture).Obtained mixture is subjected to extruding pelletization, screw rod by double screw extruder
Revolving speed control be 10rpm, torque 20N*m, the temperature of each section is successively from feed inlet to extrusion in double screw extruder
For 160 DEG C, 170 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 170 DEG C, polymer blend A5 is made.
Embodiment 6
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
(rate of stirring is 30rpm, time 10min) under stirring conditions, by terephthalic acid (TPA) butanediol-fourth two
Sour butanediol copolyester (weight average molecular weight 100,000, wherein with terephthalic acid (TPA) butanediol repetitive unit and succinic acid fourth
On the basis of the total mole number of diol repeat units, the content of terephthalic acid (TPA) butanediol repetitive unit is 40 moles of %), to benzene two
Formic acid butanediol-adipic acid butanediol copolyester (is purchased from BASF AG, trade mark ecoflex, wherein with terephthalic acid (TPA)
On the basis of the total mole number of butanediol repetitive unit and adipic acid butanediol repetitive unit, terephthalic acid (TPA) butanediol repetitive unit
Content be 50 moles of %) and poly butylene succinate mixed according to the molar ratio of 90:1:9, and addition 5 weight % it is low
Density polyethylene (on the basis of the total weight of mixture, is purchased from middle petrochemical industry Yanshan Petrochemical company, trade mark LD607).It will obtain
Mixture by double screw extruder carry out extruding pelletization, screw rod revolving speed control be 10rpm, torque 20N*m, twin-screw
The temperature of each section is followed successively by 160 DEG C, 170 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 170 from feed inlet to extrusion in extruder
DEG C, polymer blend A6 is made.
Embodiment 7
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
Polymer blend is prepared according to the method for embodiment 1, the difference is that being added without carbonic acid used in embodiment 1
Polymer blend A7 is made in calcium.
Embodiment 8
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
Polymer blend is prepared according to the method for embodiment 1, the difference is that using the terephthalic acid (TPA) of same molar
Ethylene glycol-succinic acid glycol copolyester (weight average molecular weight 100,000, wherein with terephthalate repetitive unit
On the basis of the total mole number of succinic acid ethylene glycol repeat units, the content of terephthalate repetitive unit is rubbed for 50
You are %) terephthalic acid (TPA) butanediol-succinic acid butanediol copolyester used in embodiment 1 is replaced, polymer blend A8 is made.
Embodiment 9
The present embodiment is for illustrating polymer blend provided by the invention and preparation method thereof.
Prepare polymer blend according to the method for embodiment 1, the difference is that using same molar poly-succinic oneself
Diol ester (being prepared according to method disclosed in CN104039865B, weight average molecular weight 100,000) replaces making in embodiment 1
Polymer blend A9 is made in poly butylene succinate.
Test case
Polymer blend made from embodiment 1-9 and comparative example 1-4 is respectively prepared punching press batten, and by manufactured punching press
Batten carries out formative memory performance test, as a result as shown in table 1 below.
Table 1
| Batten material | Deformation fixed rate (%) | Shape recovery rate (%) | Largest deformation rate (%) | |
| Test case 1 | A1 | 100 | 100 | 1200 |
| Test case 2 | D1 | 82 | 0 | 30 |
| Test case 3 | D2 | 83 | 0 | 45 |
| Test case 4 | D3 | 80 | 95 | 950 |
| Test case 5 | D5 | 76 | 0 | 50 |
| Test case 6 | A2 | 99 | 98 | 700 |
| Test case 7 | A3 | 100 | 99 | 1400 |
| Test case 8 | A4 | 100 | 99 | 1600 |
| Test case 9 | A5 | 100 | 99 | 1500 |
| Test case 10 | A6 | 100 | 99 | 1500 |
| Test case 11 | A7 | 98 | 99 | 1800 |
| Test case 12 | A8 | 95 | 92 | 400 |
| Test case 13 | A9 | 100 | 100 | 1200 |
Shape-memory material will be used for by the polymer blend that embodiment 1-9 is prepared above, the shape-memory material
Deformation fixed rate and shape recovery rate reach 92% or more, largest deformation rate is up to 400% or more.In addition, the shape is remembered
Initial figuration temperature and the start-up temperature for recalling material are adjustable, this would be even more beneficial to its application in daily life.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (21)
1. a kind of polymer blend, which is characterized in that the polymer blend includes:
(1) polyester A, the polyester A are the copolymerization containing repetitive unit B shown in repetitive unit A shown in formula (I) and formula (II)
Object,
(2) polyester B, the polyester B are being total to containing repetitive unit B shown in repetitive unit C shown in formula (III) and formula (II)
Polymers,
(3) aliphatic polyester,
Wherein, m1 is the integer of 2-6, and n1 is the integer of 2-4, and m1 and n1 are identical or different, the weight average molecular weight of the polyester A
For 100,000-500,000；M2 is the integer of 2-6, and n2 is the integer of 2-4, and m2 and n2 are identical or different, the polyester B's
Weight average molecular weight is 100,000-500,000；Also, n1 is less than n2；
On the basis of the total mole number of the polyester A, the polyester B and the aliphatic polyester, the content of the repetitive unit B
For 5-49 moles of %；
The aliphatic polyester contains repetitive unit D shown in formula (VI),
The m3 is the integer of 2-6, and n3 is the integer of 2-4, and m3 and n3 are identical or different, and the aliphatic polyester is divided equally again
Son amount is 100,000-500,000；
The molar ratio of the polyester A, the polyester B and the aliphatic polyester is 20-90:1-90:1-20.
2. polymer blend according to claim 1, wherein with the polyester A, the polyester B and the aliphatic poly
On the basis of the total mole number of ester, the content of the repetitive unit B is 20-40 moles of %.
3. polymer blend according to claim 1 or 2, wherein with repetitive unit A and repetitive unit B in the polyester A
Total mole number on the basis of, the content of the repetitive unit A is 40-95 moles of %；The content of the repetitive unit B is rubbed for 5-60
You are %；
On the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B, the content of the repetitive unit C is
40-95 moles of %；The content of the repetitive unit B is 5-60 moles of %.
4. polymer blend according to claim 3, wherein with repetitive unit A and repetitive unit B in the polyester A
On the basis of total mole number, the content of the repetitive unit A is 45-90 moles of %；The content of the repetitive unit B is rubbed for 10-55
You are %；
On the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B, the content of the repetitive unit C is
50-90 moles of %；The content of the repetitive unit B is 10-50 moles of %.
5. polymer blend according to claim 1 or 2, wherein the polyester A, the polyester B and the aliphatic poly
The molar ratio of ester is 20-90:1-70:1-20.
6. polymer blend according to claim 1 or 2, wherein the polymer blend also contains nucleating agent；With described
On the basis of the total weight of polymer blend, the content of the nucleating agent is 0.01-20 weight %.
7. polymer blend according to claim 6, wherein described on the basis of the total weight of the polymer blend
The content of nucleating agent is 0.2-5 weight %.
8. polymer blend according to claim 7, wherein the nucleating agent be selected from talcum powder, calcium oxide, calcium carbonate,
Inorganic pigment, kaolin, carboxylic metallic salt, phosphate metal salt, dibenzyl sorbierite and its derivative, gather polyvinyl eyclohexane
One or more of ethylene pentane, low density polyethylene (LDPE), ultrabranching polyamide and ethylene-methyl methacrylate ionomer.
9. polymer blend according to claim 8, wherein the nucleating agent is calcium carbonate, low density polyethylene (LDPE), dibenzyl
Sorbierite and its one or more of derivative and ultrabranching polyamide.
10. a kind of preparation method of polymer blend, which is characterized in that this method comprises: by polyester A, polyester B and aliphatic poly
Ester mixing, and obtained mixture is subjected to extruding pelletization, to obtain polymer blend；
The polyester A is the copolymer containing repetitive unit B shown in repetitive unit A shown in formula (I) and formula (II),
The polyester B is the copolymer containing repetitive unit B shown in repetitive unit C shown in formula (III) and formula (II),
Wherein, m1 is the integer of 2-6, and n1 is the integer of 2-4, and m1 and n1 are identical or different, the weight average molecular weight of the polyester A
For 100,000-500,000；M2 is the integer of 2-6, and n2 is the integer of 2-4, and m2 and n2 are identical or different, the polyester B's
Weight average molecular weight is 100,000-500,000；Also, n1 is less than n2；
On the basis of the total mole number of the polyester A, the polyester B and the aliphatic polyester, the content of the repetitive unit B
For 5-49 moles of %；
The aliphatic polyester contains repetitive unit D shown in formula (VI),
The m3 is the integer of 2-6, and n3 is the integer of 2-4, and m3 and n3 are identical or different, and the aliphatic polyester is divided equally again
Son amount 100,000-500,000；
The molar ratio of the dosage of the polyester A, the polyester B and the aliphatic polyester is 20-90:1-90:1-20.
11. according to the method described in claim 10, wherein, with the polyester A, the polyester B and the aliphatic polyester
On the basis of total mole number, the content of the repetitive unit B is 10-45 moles of %.
12. method described in 0 or 11 according to claim 1, wherein with repetitive unit A and repetitive unit B in the polyester A
On the basis of total mole number, the content of the repetitive unit A is 40-95 moles of %；The content of the repetitive unit B is rubbed for 5-60
You are %；
On the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B, the content of the repetitive unit C is
40-95 moles of %；The content of the repetitive unit B is 5-60 moles of %.
13. according to the method for claim 12, wherein always rubbed with repetitive unit A and repetitive unit B in the polyester A
On the basis of your number, the content of the repetitive unit A is 45-90 moles of %；The content of the repetitive unit B is 10-55 moles of %；
On the basis of the total mole number of repetitive unit C and repetitive unit B in the polyester B, the content of the repetitive unit C is
50-90 moles of %；The content of the repetitive unit B is 10-50 moles of %.
14. method described in 0 or 11 according to claim 1, wherein the polyester A, the polyester B and the aliphatic polyester
Dosage molar ratio be 20-90:1-70:1-20.
15. method described in 0 or 11 according to claim 1, wherein this method comprises: by polyester A, polyester B, aliphatic polyester
It is carried out in the presence of nucleating agent with the process of nucleating agent mixing；On the basis of the total weight of the polymer blend, it is described at
The dosage of core agent is 0.01-20 weight %.
16. according to the method for claim 15, wherein on the basis of the total weight of the polymer blend, the nucleation
The dosage of agent is 0.2-5 weight %.
17. according to the method for claim 16, wherein the nucleating agent is selected from talcum powder, calcium oxide, calcium carbonate, inorganic
Pigment, kaolin, carboxylic metallic salt, phosphate metal salt, dibenzyl sorbierite and its derivative, polyvinyl eyclohexane, polyethylene
One or more of pentane, low density polyethylene (LDPE), ultrabranching polyamide and ethylene-methyl methacrylate ionomer.
18. according to the method for claim 17, wherein the nucleating agent is calcium carbonate, low density polyethylene (LDPE), dibenzyl mountain
Pears alcohol and its one or more of derivative and ultrabranching polyamide.
19. method described in any one of 0 or 11 according to claim 1, wherein it is described mixing under stirring conditions into
Row；Also, the rate of the stirring is 6-60rpm, and the time of the stirring is 2-30min；
The extruding pelletization carries out in double screw extruder；The condition of the extruding pelletization includes: that temperature is 160-220 DEG C,
Screw speed is 10-70rpm, torque 2-80N*m.
20. the polymer blend that the method as described in any one of claim 10-19 is prepared.
21. polymer blend described in any one of claim 1-9 and 20 is applied in shape-memory material.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610922101.3A CN107974052B (en) | 2016-10-21 | 2016-10-21 | A kind of polymer blend and its preparation method and application |
| US16/343,711 US11466151B2 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| CA3040988A CA3040988A1 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| EP17862862.4A EP3530694A4 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| PCT/CN2017/107106 WO2018072746A1 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| JP2019520899A JP7584219B2 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, its production method and its application |
| JP2024130717A JP2024155925A (en) | 2016-10-21 | 2024-08-07 | Polyester composition, its production method and its application |
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| CN109401211B (en) * | 2017-08-16 | 2022-12-13 | 中国石油化工股份有限公司 | Polyester composition, medical limb fixing support and preparation method thereof |
| CN109401212B (en) * | 2017-08-16 | 2022-12-13 | 中国石油化工股份有限公司 | Polyester composition, heat-shrinkable film and process for producing the same |
| US11466151B2 (en) | 2016-10-21 | 2022-10-11 | China Petroleum & Chemical Corporation | Polyester composition, preparation method therefor and application thereof |
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| US7557167B2 (en) * | 2006-09-28 | 2009-07-07 | Gore Enterprise Holdings, Inc. | Polyester compositions, methods of manufacturing said compositions, and articles made therefrom |
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| CN1537134A (en) * | 2001-08-01 | 2004-10-13 | �����Ű�̩��Ƭ�ϻ�������˾ | Conformable copolyester film |
| CN101098932A (en) * | 2005-01-12 | 2008-01-02 | 巴斯福股份公司 | Biologically-degradable polyester mixture |
| JP2012205552A (en) * | 2011-03-30 | 2012-10-25 | C I Kasei Co Ltd | Biodegradable mulching film |
| CN102838854A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Biodegradable composite, disposable product and preparation method thereof |
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