CN106633807A - TPU (thermoplastic polyurethane) film with temperature-control color change function, method for preparing TPU film and application thereof - Google Patents
TPU (thermoplastic polyurethane) film with temperature-control color change function, method for preparing TPU film and application thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C08J5/18—Manufacture of films or sheets
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- C08L75/08—Polyurethanes from polyethers
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2375/08—Polyurethanes from polyethers
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Abstract
The invention provides a TPU (thermoplastic polyurethane) film with a temperature-control color change function, a method for preparing the TPU film and application thereof. The TPU film with the temperature-control color change function mainly comprises, by weight, 60-70% of TPU particles, 12-13% of phosphite without benzene rings, 10-13% of hydrogen-containing silicone oil, 2-8% of white carbon black, 1-5% of nanometer barium titanate and 1-9% of antioxidants. The TPU particles comprise TPU molecular chains and peptide side-chain polydiacetylene grafted onto the TPU molecular chains. The TPU film, the method and the application have the advantages that the TPU film has a temperature-control color change characteristic, the color change speed of 1 s, the melt index of 22-25 g/10 min, the yellowing-resistant performance at 5 grade, the tear strength of 46-49 kgf and the tensile strength of 47-51 MPa, and is a TPU film with excellent comprehensive performance; the TPU film can be used as a functional material to be applied to high-grade building coatings, stick films on windows of trains and automobiles, shoe materials and the like, accordingly, illumination or heat exchange can be adjusted, and the aesthetics and the diversity can be improved.
Description
Technical field
The invention belongs to TPU film preparing technical field, and in particular to a kind of TPU film and its preparation method and application,
More particularly to it is a kind of can temperature-control discoloring TPU film and its preparation method and application.
Background technology
TPU (Thermoplastic polyyrethane, thermoplastic polyurethane) is that a kind of new organic polymer is closed
Into material, belong to compound, English trade name：Flexible polyurethane, are that a kind of properties are excellent, Ke Yidai
For rubber rubber, soft polyvinyl chloride material PVC.For example it has excellent physical property, such as wearability, and screen resilience is all
Well conventional polyurethanes, PVC, resistance to ag(e)ing is better than rubber, it may be said that be the optimal material for substituting PVC and PU, international
It is upper to be referred to as novel polymer material.
Polyurethane termoplastic elastomer has polyester-type and a class of polyether-type two, white random spherical or cylindrical particle, relatively
Density 1.10-1.25, polyether-type relative density is less than polyester-type.The characteristics of polyurethane termoplastic elastomer is projected is that wearability is excellent
Different, ozone resistance is fabulous, hardness is big, intensity is high, elasticity is good, low temperature resistant, there is good oil resistant, chemical-resistant resistance and environment resistant
Can, polyether-type ester hydrolysis stability exceeds well over polyester-type in wet environment.
The application of TPU film is now more and more extensive.TPU film can be applicable to top-grade building overlay film, automobile and train car
Pad pasting, footwear material of window etc..However, can temperature-control discoloring TPU film research it is also rarely found, can temperature-control discoloring TPU film lead to
The adjustable illumination of temperature-control discoloring or heat exchange are crossed, while increasing aesthetic feeling and diversity.
The content of the invention
It is an object of the invention to provide a kind of a kind of specifically related to TPU film and its preparation method and application, especially relates to
And it is a kind of can temperature-control discoloring TPU film and its preparation method and application.The present invention by being modified to molecular structure, by one
Fixed method, peptide side chain polybutadiene alkynes is grafted in TPU strands, obtains new TPU materials, is capable of achieving temperature-control discoloring.
It is that, up to this purpose, the present invention is employed the following technical solutions：
On the one hand, the invention provides it is a kind of can temperature-control discoloring TPU film, mainly contain by weight/mass percentage composition following
Component：
Wherein TPU particles include TPU strands and the peptide side chain polybutadiene alkynes being grafted on TPU strands.
The chain molecule that peptide is made up of amino acid, is also composition indispensable in inanimate object protein.This TPU
Particle is a kind of to be processed into variously-shaped nanofiber.Extrusion fiber can be passed through；Film is formed by coating；Also can mould
Molded hydrogel.
It is of the present invention can be in the TPU film of temperature-control discoloring, the molecular weight of the peptide is 1000-3000, such as 1000,
1500th, 2000,2500 or 3000.
It is of the present invention can be in the TPU film of temperature-control discoloring, the quality percentage of side chain polybutadiene alkynes in the TPU particles
Content is 15-20%, such as 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%
Or 20%.
It is of the present invention can be in the TPU film of temperature-control discoloring, the method for the grafting is：By diacetylene, TPU and crosslinking
Agent reacts 0.5-5h at 225-250 DEG C.For example reaction temperature can for 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C or
250 DEG C, the reaction time is 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h.
It is of the present invention can be in the TPU film of temperature-control discoloring, the crosslinking agent is the methylimidazole of 2- ethyls -4,2- isopropyls
One or two in base imidazoles, hexahydrophthalic anhydride, trien, DIMAPA, diethyl amino propylamine
Mixing above.
Preferably, the weight/mass percentage composition of the crosslinking agent for TPU particles 0.5-3%, such as 0.5%, 1%,
1.3%th, 1.5%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8% or 3%.
It is of the present invention can be in the TPU film of temperature-control discoloring, the TPU granule contents are 60-70%, such as 61%,
62%th, 63%, 64%, 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5% or
70%.
Preferably, the TPU particles are one or two mixing in polyether-type TPU particles and polyester-type TPU particles.
It is of the present invention can be in the TPU film of temperature-control discoloring, the content of the phosphite ester without phenyl ring is 12-
13%, such as 12%, 12.2%, 12.4%, 12.6%, 12.8% or 13%.
It is of the present invention can be in the TPU film of temperature-control discoloring, the content of the containing hydrogen silicone oil is 10-13%, for example
10%th, 10.3%, 10.5%, 10.8%, 11%, 11.3%, 11.5%, 11.8%, 12%, 12.2%, 12.4%,
12.6%th, 12.8% or 13%.
It is of the present invention can be in the TPU film of temperature-control discoloring, the content of the white carbon is 2-8%, such as 2%,
2.3%th, 2.5%, 2.8%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%.
It is of the present invention can be in the TPU film of temperature-control discoloring, the content of the antioxidant is 1-5%, such as 1%,
1.3%th, 1.5%, 1.8%, 2%, 2.4%, 2.8%, 3%, 3.5%, 3.8%, 4%, 4.5%, 4.8%, 5%, 5.5%,
6%th, 6.5%, 7%, 7.5%, 8%, 8.5% or 9%.
On the other hand, the invention provides as described in relation to the first aspect can temperature-control discoloring TPU film preparation method, bag
Include following steps：
(1) all components are pre-dried；
(2) all dried components are mixed, Jing casting machine extrusion moldings obtain final product the TPU film.
It is of the present invention can temperature-control discoloring TPU film preparation method in, the temperature of step (1) drying is 85
～105 DEG C, such as 85 DEG C, 87 DEG C, 90 DEG C, 93 DEG C, 95 DEG C, 98 DEG C, 100 DEG C, 103 DEG C or 105 DEG C, dry time is 2～
3h, such as 2h, 2.2h, 2.4h, 2.6h, 2.7h, 2.8h, 2.9h or 3h.
It is of the present invention can temperature-control discoloring TPU film preparation method in, each section of temperature of step (2) casting machine
Degree arranges as follows：Barrel temperature be 150-230 DEG C, such as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C,
220 DEG C or 230 DEG C；Filter screen temperature is 170-210 DEG C, such as 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C or 210 DEG C；Elbow temperature
For 170-210 DEG C, such as 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C or 210 DEG C；Die head temperature be 180-220 DEG C, such as 180 DEG C,
190 DEG C, 200 DEG C, 210 DEG C or 220 DEG C.
On the other hand, the invention provides as described in relation to the first aspect can temperature-control discoloring TPU film in functional material
The application in field.The TPU film of the present invention can be used as top-grade building overlay film, automobile and train vehicle window as functional material
Pad pasting, footwear material etc..Can temperature-control discoloring TPU film by the adjustable illumination of temperature-control discoloring or heat exchange, while increasing aesthetic feeling
And diversity.
Relative to prior art, the invention has the advantages that：
TPU film prepared by the present invention have can temperature-control discoloring characteristic, color change is 1s, and with 22-25g/
The melt index of 10min, anti-yellowing property be 5 grades, tearing strength is 46-49kgf, and tensile strength is 47-51MPa, i.e., this
The TPU film of bright preparation have it is good can temperature-control discoloring characteristic, good anti-yellowing property and good mechanical performance, be
A kind of TPU film with excellent comprehensive performance, the obtained TPU film of the present invention can be applied to top grade as functional material
Pad pasting, footwear material of building overlay film, automobile and train vehicle window etc., by the adjustable illumination of temperature-control discoloring or heat exchange, while increasing
Aesthetic feeling and diversity.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
In the present embodiment, can temperature-control discoloring TPU film, contain following components by weight/mass percentage composition：
Wherein TPU particles include TPU strands and the peptide side chain polybutadiene alkynes being grafted on TPU strands, will account for TPU
The grain diacetylene of weight/mass percentage composition 15%, TPU particles and account for the crosslinking agent 2- ethyls of TPU granular mass percentage composition 0.5%-
4 methylimidazoles react 0.5h at 235 DEG C and peptide side chain polybutadiene alkynes are grafted on TPU strands；The molecule of wherein described peptide
Measure as 2000.
It is described can temperature-control discoloring TPU film using following methods prepare：
(1) all components are pre-dried into 2h at 90 DEG C；
(2) all dried components are mixed, Jing casting machine extrusion moldings obtain final product the TPU film；
Each section of temperature setting of the casting machine is as follows：Barrel temperature is 170 DEG C；Filter screen temperature is 170 DEG C；Elbow temperature
For 200 DEG C；Connection temperature is 200 DEG C；Die head temperature is 210 DEG C.
Embodiment 2
In the present embodiment, can temperature-control discoloring TPU film, contain following components by weight/mass percentage composition：
Wherein TPU particles include TPU strands and the peptide side chain polybutadiene alkynes being grafted on TPU strands；TPU will be accounted for
The grain diacetylene of weight/mass percentage composition 20%, TPU particles and account for crosslinking agent hexahydro neighbour's benzene of TPU granular mass percentage composition 1%
Dicarboxylic acid anhydride reacts 2.5h at 250 DEG C and peptide side chain polybutadiene alkynes is grafted on TPU strands；The molecular weight of wherein described peptide
For 1000.
It is described can temperature-control discoloring TPU film using following methods prepare：
(1) all components are pre-dried into 3h at 85 DEG C；
(2) all dried components are mixed, Jing casting machine extrusion moldings obtain final product the TPU film, the casting machine
Each section of temperature setting it is as follows：Barrel temperature is 150 DEG C；Filter screen temperature is 170 DEG C；Elbow temperature is 210 DEG C；Connecting temperature is
210℃；Die head temperature is 220 DEG C.
Embodiment 3
In the present embodiment, can temperature-control discoloring TPU film, contain following components by weight/mass percentage composition：
Wherein TPU particles include TPU strands and the peptide side chain polybutadiene alkynes being grafted on TPU strands；TPU will be accounted for
The grain diacetylene of weight/mass percentage composition 18%, TPU particles and account for the crosslinking agent diethylin of TPU granular mass percentage composition 3%
Propylamine reacts 5h at 225 DEG C and peptide side chain polybutadiene alkynes is grafted on TPU strands；The molecular weight of wherein described peptide is
3000。
It is described can temperature-control discoloring TPU film using following methods prepare：
(1) all components are pre-dried into 2.5h at 105 DEG C；
(2) all dried components are mixed, Jing casting machine extrusion moldings obtain final product the TPU film；
Each section of temperature setting of the casting machine is as follows：Barrel temperature is 230 DEG C；Filter screen temperature is 170 DEG C；Elbow temperature
For 210 DEG C；Connection temperature is 210 DEG C；Die head temperature is 220 DEG C.
Embodiment 4
In the present embodiment, can temperature-control discoloring TPU film, contain following components by weight/mass percentage composition：
Wherein TPU particles include TPU strands and the peptide side chain polybutadiene alkynes being grafted on TPU strands；TPU will be accounted for
The grain diacetylene of weight/mass percentage composition 17%, TPU particles and account for the crosslinking agent diethylin of TPU granular mass percentage composition 3%
Propylamine reacts 4h at 240 DEG C and peptide side chain polybutadiene alkynes is grafted on TPU strands；The molecular weight of wherein described peptide is
3000。
It is described can temperature-control discoloring TPU film using following methods prepare：
(1) all components are pre-dried into 5h at 100 DEG C；
(2) all dried components are mixed, Jing casting machine extrusion moldings obtain final product the TPU film；
Each section of temperature setting of the casting machine is as follows：Barrel temperature is 150 DEG C；Filter screen temperature is 170 DEG C；Elbow temperature
For 210 DEG C；Connection temperature is 210 DEG C；Die head temperature is 210 DEG C.
Comparative example 1
The fourth that comparative example 1 is added as different from Example 1 when peptide side chain polybutadiene alkynes is grafted on TPU strands
Diine accounts for TPU granular mass percentage composition for 14%, remaining raw material and raw material dosage and preparation method and condition with enforcement
Example 1 is identical.
Comparative example 2
The fourth that comparative example 2 is added as different from Example 1 when peptide side chain polybutadiene alkynes is grafted on TPU strands
Diine accounts for TPU granular mass percentage composition for 21%, remaining raw material and raw material dosage and preparation method and condition with enforcement
Example 1 is identical.
Comparative example 3
It is 58% that comparative example 3 prepares as different from Example 2 the consumption of TPU particles in the raw material of TPU film, Silicon Containing Hydrogen
The consumption of oil is 12%, and remaining raw material dosage and preparation method are same as Example 1.
Comparative example 4
It is 72% that comparative example 4 prepares as different from Example 3 the consumption of TPU particles in the raw material of TPU film, Silicon Containing Hydrogen
The consumption of oil is 11%, and remaining raw material and raw material dosage and preparation method and condition are same as Example 3.
Comparative example 5
Comparative example 5 prepares as different from Example 1 the consumption of the phosphite ester without phenyl ring in the raw material of TPU film
The consumption of 15%, TPU particle is 63%, and remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 6
It is 9%, TPU that comparative example 6 prepares as different from Example 3 the consumption of containing hydrogen silicone oil in the raw material of TPU film
The consumption of grain is 67%, and remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 7
It is 10% that comparative example 7 prepares as different from Example 2 the consumption of white carbon in the raw material of TPU film, antioxidant
Consumption is 7%, and remaining raw material and raw material dosage and preparation method and condition are same as Example 2.
Comparative example 8
It is 7%, TPU that comparative example 8 prepares as different from Example 1 the consumption of nano barium phthalate in the raw material of TPU film
The consumption of particle is 63%, and remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 9
It is 0.5% that comparative example 9 prepares as different from Example 3 the consumption of nano barium phthalate in the raw material of TPU film, nothing
The consumption of the phosphite ester of phenyl ring is 12.5%, remaining raw material and raw material dosage and preparation method and condition with embodiment 3
It is identical.
Performance evaluation is carried out to TPU film obtained in embodiment 1-4 and comparative example 1-9, it is as a result as shown in table 1 below.
Table 1
As shown in Table 1, the present invention prepare TPU film have can temperature-control discoloring characteristic, color change is 1s, and is had
There is the melt index of 22-25g/10min, anti-yellowing property is 5 grades, and tearing strength is 46-49kgf, and tensile strength is 47-
51MPa, i.e., the TPU film that prepared by the present invention have it is good can temperature-control discoloring characteristic, good anti-yellowing property and good
Mechanical performance, be a kind of TPU film with excellent mechanical properties, and when in the raw material for preparing TPU film certain component use
When outside the present invention limits scope (comparative example 1-9), the properties of the TPU film for preparing are decreased obviously amount, and this says
It is bright, cooperate between each component in the present invention, generate good effect.Obtained TPU film of the invention can be used as work(
Energy property material, is applied to top-grade building overlay film, the pad pasting of automobile and train vehicle window, footwear material etc..The adjustable illumination of temperature-control discoloring or
Heat exchange, while increasing aesthetic feeling and diversity.
Applicant state, the present invention illustrated by above-described embodiment the present invention can temperature-control discoloring TPU film and its
Preparation method and application, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention has to rely on above-mentioned enforcement
Example could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, to each original of product of the present invention
The equivalence replacement of material and the addition of auxiliary element, the selection of concrete mode etc., all fall within protection scope of the present invention and open model
Within enclosing.
Claims (10)
1. it is a kind of can temperature-control discoloring TPU film, it is characterised in that mainly contain following components by weight/mass percentage composition：
Wherein TPU particles include TPU strands and the peptide side chain polybutadiene alkynes being grafted on TPU strands.
2. TPU film according to claim 1, it is characterised in that the molecular weight of the peptide is 1000-3000.
3. TPU film according to claim 1 and 2, it is characterised in that the matter of side chain polybutadiene alkynes in the TPU particles
Amount percentage composition is 15-20%.
4. the TPU film according to any one of claim 1-3, it is characterised in that the method for the grafting is：By fourth two
Alkynes, TPU and crosslinking agent react 0.5-5h at 225-250 DEG C.
5. TPU film according to claim 4, it is characterised in that the crosslinking agent is the methylimidazole of 2- ethyls -4,2- different
One kind in propyl imidazole, hexahydrophthalic anhydride, trien, DIMAPA, diethyl amino propylamine or two
Plant the mixing of the above；
Preferably, the weight/mass percentage composition of the crosslinking agent is the 0.5-3% of TPU particles.
6. the TPU film according to any one of claim 1-5, it is characterised in that the TPU particles are polyether-type TPU
One or two mixing in grain and polyester-type TPU particles.
7. described in a kind of any one of claim 1-6 can temperature-control discoloring TPU film preparation method, comprise the steps：
(1) all components are pre-dried；
(2) all dried components are mixed, Jing casting machine extrusion moldings obtain final product the TPU film.
8. preparation method according to claim 7, it is characterised in that the temperature of step (1) drying is 85～105
DEG C, the dry time is 2～3h.
9. the preparation method according to claim 7 or 8, it is characterised in that each section of temperature of step (2) casting machine sets
Put as follows：Barrel temperature is 150-230 DEG C；Filter screen temperature is 170-210 DEG C；Elbow temperature is 170-210 DEG C；Die head temperature is
180-220℃。
10. according to any one of claim 1-6 can temperature-control discoloring TPU film functional material field should
With.
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| CN201610920797.6A CN106633807A (en) | 2016-10-21 | 2016-10-21 | TPU (thermoplastic polyurethane) film with temperature-control color change function, method for preparing TPU film and application thereof |
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| CN105199370A (en) * | 2015-10-29 | 2015-12-30 | 无锡市嘉邦电力管道厂 | TPU (thermoplastic polyurethane) film capable of realizing temperature-control color change as well as preparation method and application of TPU film |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448789A (en) * | 2014-12-12 | 2015-03-25 | 东莞市雄林新材料科技股份有限公司 | Temperature-controllable thermochromic TPU (thermoplastic polyurethane) film and preparation method thereof |
| CN105199370A (en) * | 2015-10-29 | 2015-12-30 | 无锡市嘉邦电力管道厂 | TPU (thermoplastic polyurethane) film capable of realizing temperature-control color change as well as preparation method and application of TPU film |
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