CN105111398B - One kind having shape memory function TPU film and preparation method thereof - Google Patents
One kind having shape memory function TPU film and preparation method thereof Download PDFInfo
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The present invention provides one kind to have shape memory function TPU film and preparation method thereof, and the TPU film is mainly prepared by the following raw material in parts by weight: 30-46 parts of terminal hydroxy group polyethylene；8-16 parts of fluorine-containing polyether glycol；21-33 parts of polyether Glycols；23-32 parts of aliphatic diisocyanate；3-5 parts of chain extender.Transfer of shapes temperature provided by the invention with shape memory function TPU film is 15-25 DEG C, and recovery of shape temperature is 40-55 DEG C；The TPU film passes through change temperature after there is high resiliency, shape to change within the temperature range of 40-75 DEG C can make it rapidly be returned to original shape；The shape fixed rate with shape memory function TPU film reaches as high as 98%, and shape recovery rate reaches as high as 99%；And preparation method is simple, is suitble to large-scale production.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly to it is a kind of have shape memory function TPU film and its
Preparation method.
Background technique
Shape-memory polymer refers to the high molecular material with shape memory characteristic, its initial configuration is solid by deformation
After fixed, by the stimulation of the external conditions such as heat, light, electricity, pH value or phase transition, it is returned to its initial configuration.When temperature is higher than glass
When glass transition temperature, polyurethane material can change, deformed when temperature is reduced to glass transition temperature or less
Shape is fixed；When temperature is increased again to glass transition temperature or more, material can reply original shape.
It is converted between original-shape and various temporary shapes that thermo-stimulative shape memory polymer material can be set at one
Basic principle is the fixation of its temporary shapes and releasing can be changed by high molecular phase (crystalline state and molten state or glassy state with
Elastomeric state) it is realized to control.Traditional thermo-stimulative shape memory polymer material is mainly shape memory copolymer material and shape
Remember blend material.Current most of commercialized shape memory high molecule materials are come in a manner of the chemical synthesis of combined polymerization
Preparation.The synthesis process of these shape memory copolymer materials is extremely complex, and higher cost, practicability is low, simultaneously as needing
A large amount of inflammable and toxicity organic solvents are used, causes safety low, larger pollution is caused to environment, are difficult to realize extensive
Production.Although and traditional shape memory blend material preparation process more simplifies, and it is poly- only to work as two kinds be mutually mixed
When closing the phase structure of object formation co-continuous, that is, only when the component ratio for the two kinds of polymer being mutually mixed is near 50:50
When, just there are preferable shape-memory properties.The performance of resulting materials is relatively limited, and the adjustable extent of performance is very narrow
It is small.In addition, this kind of shape memory high molecule materials prepared by conventional physical blend method there is also memory performances can be with making
The problem of being weakened with the increase of number.Therefore, raw material that is suitable and easily obtaining is selected, cooperates easy preparation method, comes high
Efficiency designs and prepares the focus technology problem that the shape memory high molecule material haveing excellent performance is field development.
CN 102408539A provides a kind of shape memory polyurethane, by ratio of weight and the number of copies mainly by 10-20 parts of end hydroxyl
Base dimethyl silicone polymer, 15-40 parts of methyl diphenylene diisocyanate, 45-60 parts of polyethylene glycol and the 1 of 5-12 parts,
4- butanediol is made, and wherein hydroxyl-terminated injecting two methyl siloxane distribution is 1000-6000, preferred range in 2000-5000,
Polyethylene glycol range of choice is 1000-4000.But this polyurethane material is prepared using solution reaction, process is cumbersome, and
The shape memory polyurethane performance arrived is not good enough.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide one kind to have shape memory function TPU thin
Film and preparation method thereof, the shape memory function TPU film.
To achieve this purpose, the present invention adopts the following technical scheme:
One kind having shape memory function TPU film, and the TPU film is mainly prepared by the following raw material in parts by weight
It arrives:
It is mainly prepared in parts by weight by the following raw material with shape memory function TPU film: terminal hydroxy group polyethylene
30-46 parts, such as 32 parts, 33 parts, 35 parts, 38 parts, 40 parts, 42 parts or 45 parts；8-16 parts of fluorine-containing polyether glycol, such as 9 parts, 10
Part, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.；21-33 parts of polyether Glycols, such as 22 parts, 23 parts, 24 parts, 25 parts, 26 parts,
27 parts, 28 parts, 29 parts, 30 parts, 31 parts or 32 parts etc.；23-32 parts of aliphatic diisocyanate, such as 25 parts, 26 parts, 27 parts, 28
Part, 29 parts, 30 parts or 31 parts etc.；3-5 parts of chain extender, such as 3 parts, 4 parts or 5 parts.
The TPU film is mainly prepared by the following raw material in parts by weight as a preferred technical solution:
Technical solution more preferably, the TPU film are mainly prepared by the following raw material in parts by weight:
The number-average molecular weight of the terminal hydroxy group polyethylene be 10000-60000, such as 11000,15000,20000,30000,
35000,40000,45000,50000 or 55000 etc..The terminal hydroxy group polyethylene is preferably line style terminal hydroxy group polyethylene or branching
Small terminal hydroxy group polyethylene is spent, the Chain Flexibility of these two types of terminal hydroxy group polyethylene is larger, and glass transition temperature is lower.
The degree of functionality of the fluorine-containing polyether glycol is 2.02-2.05, such as 2.03,2.04 or 2.05.Due to terminal hydroxy group
The Chain Flexibility of polyethylene is larger, therefore a small amount of fluorine-containing polyether glycol is added in polyurethane molecular chain, can be appropriate
Ground improves the interaction between TPU strand, and makes have a small amount of branch in product TPU, improves the crystallinity of TPU hard section
Energy.
Preferably, the number-average molecular weight of the fluorine-containing polyether glycol be 5000-10000, such as 5500,6000,6500,
7000,8000,9000 or 9500 etc..
The number-average molecular weight of the polyether Glycols be 6000-20000, such as 6500,7000,7500,8000,9000,
10000,12000,15000,17000 or 19000 etc..
The molecular weight of the aliphatic diisocyanate is 100-1000, such as 200,300,400,600,700 or 900.
The lesser aliphatic diisocyanate of number-average molecular weight is selected, the formation of crystal region in TPU is conducive to.
The molecular weight of the chain extender is 50-200, such as 60,70,80,100,130,150,180 or 190.
Preferably, the chain extender be ethylene glycol, Isosorbide-5-Nitrae butanediol, 1,6- hexylene glycol, 1,2-PD, methyl propanediol,
One of 1,3-BDO, diglycol, 1,6- hexylene glycol or neopentyl glycol or at least two combination, it is typical but non-
Restrictive combination such as ethylene glycol and Isosorbide-5-Nitrae butanediol, 1,6- hexylene glycol, 1,2-PD and methyl propanediol, 1,3-BDO,
Diglycol, 1,6-HD and neopentyl glycol etc..
The second object of the present invention is to provide a kind of preparation method of TPU film as described above, the preparation method
Include the following steps:
(1) it will be mixed after the drying of the terminal hydroxy group polyethylene of formula ratio, fluorine-containing polyether glycol, polyether Glycols and chain extender
It closes, obtains mixed material；
(2) aliphatic diisocyanate of formula ratio is added in mixed material and is reacted；
(3) by after step (2) reaction product drying, curing and it is broken after obtain TPU particle；
(4) TPU particle is obtained through casting machine extrusion molding with shape memory function TPU film.
The temperature of step (2) described reaction is 80-100 DEG C, such as 85 DEG C, 90 DEG C, 92 DEG C, 95 DEG C, 97 DEG C or 99 DEG C, when
Between be 1-3h, such as 1h, 2h or 3h.
Preferably, the temperature of step (4) described extrusion is 180-200 DEG C, such as 182 DEG C, 183 DEG C, 185 DEG C, 187 DEG C, 190
DEG C, 192 DEG C, 195 DEG C or 197 DEG C etc..
Compared with prior art, the invention has the benefit that
Transfer of shapes temperature provided by the invention with shape memory function TPU film is 15-25 DEG C, recovery of shape temperature
Degree is 40-55 DEG C.The TPU film passes through after there is high resiliency, shape to change within the temperature range of 40-75 DEG C and changes temperature
It can be made rapidly to be returned to original shape；DMA dynamic mechanical analysis measures its shape fixed rate and reaches as high as 98%, shape
Shape response rate reaches as high as 99%.
Preparation method provided by the invention with shape memory function TPU film is simple, convenient for large-scale production.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
One kind having shape memory function TPU film, and the TPU film is mainly prepared by the following raw material in parts by weight
It arrives:
Wherein, the number-average molecular weight of the terminal hydroxy group polyethylene is 10000-15000；The degree of functionality of fluorine-containing polyether glycol
It is 2.02, number-average molecular weight 5000-8000；The number-average molecular weight of polyether Glycols is 6000-10000；Two isocyanide of aliphatic
The molecular weight of acid esters is 100-400；Chain extender is ethylene glycol.
The preparation method with shape memory function TPU film includes the following steps:
(1) baking by terminal hydroxy group polyethylene, fluorine-containing polyether glycol, polyether Glycols and the chain extender of formula ratio at 60 DEG C
It removes water in case for 24 hours, mixes later, obtain mixed material；
(2) aliphatic diisocyanate of formula ratio is added in mixed material, reacts 1- under the conditions of 80-100 DEG C
3h；
(3) product after step (2) reaction is dried under the conditions of 80 DEG C 3h, then in 85 DEG C of curing 10h, is obtained after broken
TPU particle；
(4) TPU particle obtains thin with shape memory function TPU through casting machine extrusion molding under the conditions of 180-200 DEG C
Film.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate of film, respectively up to 96% and 98%；Transfer of shapes temperature is 20 DEG C, recovery of shape temperature
Degree is 40 DEG C.The TPU film has high resiliency within the temperature range of 40-75 DEG C.
Embodiment 2
One kind having shape memory function TPU film, and the TPU film is mainly prepared by the following raw material in parts by weight
It arrives:
Wherein, the number-average molecular weight of the terminal hydroxy group polyethylene is 25000-40000；The degree of functionality of fluorine-containing polyether glycol
It is 2.04, number-average molecular weight 8000-10000；The number-average molecular weight of polyether Glycols is 15000-20000；Aliphatic two is different
The molecular weight of cyanate is 700-1000；Chain extender is the combination of diglycol, 1,6-HD and neopentyl glycol.
The preparation method with shape memory function TPU film is same as Example 1.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate of film, respectively up to 97% and 96%；Transfer of shapes temperature is 15 DEG C, recovery of shape temperature
Degree is 45 DEG C.The TPU film has high resiliency within the temperature range of 50-75 DEG C.
Embodiment 3
One kind having shape memory function TPU film, and the TPU film is mainly prepared by the following raw material in parts by weight
It arrives:
Wherein, the number-average molecular weight of the terminal hydroxy group polyethylene is 15000-25000；The degree of functionality of fluorine-containing polyether glycol
It is 2.05, number-average molecular weight 8000-10000；The number-average molecular weight of polyether Glycols is 10000-15000；Aliphatic two is different
The molecular weight of cyanate is 400-700；Chain extender is the combination of 1,4 butanediols and 1,6-HD.
The preparation method with shape memory function TPU film is same as Example 1.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate of film, respectively up to 97% and 98%；Transfer of shapes temperature is 25 DEG C, recovery of shape temperature
Degree is 55 DEG C.The TPU film has high resiliency within the temperature range of 60-75 DEG C.
Embodiment 4
One kind having shape memory function TPU film, and the TPU film is mainly prepared by the following raw material in parts by weight
It arrives:
Wherein, the number-average molecular weight of the terminal hydroxy group polyethylene is 40000-60000；The degree of functionality of fluorine-containing polyether glycol
It is 2.03, number-average molecular weight 8000-9000；The number-average molecular weight of polyether Glycols is 15000-18000；Two isocyanide of aliphatic
The molecular weight of acid esters is 700-900；Chain extender is methyl propanediol.
The preparation method with shape memory function TPU film is same as Example 1.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate of film, respectively up to 98% and 99%；Transfer of shapes temperature is 15 DEG C, recovery of shape temperature
Degree is 40 DEG C.The TPU film has high resiliency within the temperature range of 40-75 DEG C.
Comparative example 1
A kind of TPU film, the TPU film are mainly prepared by the following raw material in parts by weight:
Wherein, the number-average molecular weight of the terminal hydroxy group polyethylene is 40000-60000；The degree of functionality of fluorine-containing polyether glycol
It is 2.03, number-average molecular weight 8000-9000；The number-average molecular weight of polyether Glycols is 15000-18000；Two isocyanide of aliphatic
The molecular weight of acid esters is 700-900；Chain extender is methyl propanediol.
The preparation method of the TPU film is same as Example 1.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate highest of film are respectively 80% and 89%；Transfer of shapes temperature is 25 DEG C, recovery of shape temperature
Degree is 40 DEG C.The TPU film has high resiliency within the temperature range of 50-65 DEG C.
Comparative example 2
A kind of TPU film, the TPU film are mainly prepared by the following raw material in parts by weight:
Wherein, the number-average molecular weight of the terminal hydroxy group polyethylene is 40000-60000；The degree of functionality of fluorine-containing polyether glycol
It is 2.03, number-average molecular weight 8000-9000；The number-average molecular weight of polyether Glycols is 15000-18000；Two isocyanide of aliphatic
The molecular weight of acid esters is 700-900；Chain extender is methyl propanediol.
The preparation method of the TPU film is same as Example 1.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate highest of film are respectively 82% and 85%；Transfer of shapes temperature is 15 DEG C, recovery of shape temperature
Degree is 32 DEG C.The TPU film has high resiliency within the temperature range of 40-55 DEG C.
Comparative example 3
In addition to fluorine-containing polyether glycol is replaced with polyether polyol, remaining is same as Example 4.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate highest of film are respectively 79% and 83%；Transfer of shapes temperature is 26 DEG C, recovery of shape temperature
Degree is 39 DEG C.The TPU film has high resiliency within the temperature range of 40-55 DEG C.
Comparative example 4
In addition to polyether Glycols are replaced with polyester diol, remaining is same as Example 4.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate highest of film are respectively 80% and 83%；Transfer of shapes temperature is 18 DEG C, recovery of shape temperature
Degree is 32 DEG C.The TPU film has high resiliency within the temperature range of 45-56 DEG C.
Comparative example 5
In addition to aliphatic diisocyanate is replaced with aromatic diisocyanate, remaining is same as Example 4.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate highest of film are respectively 82% and 78%；Transfer of shapes temperature is 28 DEG C, recovery of shape temperature
Degree is 42 DEG C.The TPU film has high resiliency within the temperature range of 55-65 DEG C.
Comparative example 6
In addition to without terminal hydroxy group polyethylene, remaining is same as Example 4.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate highest of film are respectively 81% and 84%；Transfer of shapes temperature is 20 DEG C, recovery of shape temperature
Degree is 34 DEG C.The TPU film has high resiliency within the temperature range of 46-55 DEG C.
Comparative example 7
In addition to fluorine-containing polyether glycol is replaced with polyether diatomic alcohol containing fluorine, remaining is same as Example 4.
According to the DMA of ISO 6721.4: storage-tensile modulus of elasticity and the TPU that is prepared of dsc measurement method detection are thin
The shape fixed rate and shape recovery rate highest of film are respectively 85% and 82%；Transfer of shapes temperature is 19 DEG C, recovery of shape temperature
Degree is 32 DEG C.The TPU film has high resiliency within the temperature range of 42-48 DEG C.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (9)
1. one kind has shape memory function TPU film, which is characterized in that the TPU film is in parts by weight mainly by as follows
Raw material is prepared:
30-46 parts of terminal hydroxy group polyethylene
8-16 parts of fluorine-containing polyether glycol
21-33 parts of polyether Glycols
23-32 parts of aliphatic diisocyanate
3-5 parts of chain extender；
The number-average molecular weight of the terminal hydroxy group polyethylene is 10000-60000；
The degree of functionality of the fluorine-containing polyether glycol is 2.02-2.05, number-average molecular weight 5000-10000；
The number-average molecular weight of the polyether Glycols is 6000-20000.
2. TPU film according to claim 1, which is characterized in that the TPU film is in parts by weight mainly by following former
Material is prepared:
34-42 parts of terminal hydroxy group polyethylene
9-13 parts of fluorine-containing polyether glycol
25-31 parts of polyether Glycols
26-30 parts of aliphatic diisocyanate
3-5 parts of chain extender.
3. TPU film according to claim 1 or 2, which is characterized in that the TPU film is in parts by weight mainly by such as
Lower raw material is prepared:
36 parts of terminal hydroxy group polyethylene
12 parts of fluorine-containing polyether glycol
32 parts of polyether Glycols
31 parts of aliphatic diisocyanate
4 parts of chain extender.
4. TPU film according to claim 1 or 2, which is characterized in that the molecular weight of the aliphatic diisocyanate is
100-1000。
5. TPU film according to claim 1 or 2, which is characterized in that the molecular weight of the chain extender is 50-200.
6. TPU film according to claim 5, which is characterized in that the chain extender is ethylene glycol, Isosorbide-5-Nitrae butanediol, 1,2-
One of propylene glycol, methyl propanediol, 1,3 butylene glycol, diglycol, 1,6-HD or neopentyl glycol or at least
Two kinds of combination.
7. the preparation method of TPU film described in one of -6 according to claim 1, which is characterized in that the preparation method includes
Following steps:
(1) it will mix, obtain after the drying of the terminal hydroxy group polyethylene of formula ratio, fluorine-containing polyether glycol, polyether Glycols and chain extender
To mixed material；
(2) aliphatic diisocyanate of formula ratio is added in mixed material and is reacted；
(3) by after step (2) reaction product drying, curing and it is broken after obtain TPU particle；
(4) TPU particle is obtained through casting machine extrusion molding with shape memory function TPU film.
8. preparation method according to claim 7, which is characterized in that the temperature of step (2) described reaction is 80-100 DEG C,
Time is 1-3h.
9. preparation method according to claim 7 or 8, which is characterized in that the temperature of step (4) described extrusion is 180-
200℃。
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